Bimodal polyolefin production process and films therefrom

ABSTRACT

A process of producing a bimodal polyolefin composition is described, which includes in one embodiment contacting monomers with a supported bimetallic catalyst composition for a time sufficient to form a bimodal polyolefin composition that includes a high molecular weight polyolefin component and a low molecular weight polyolefin component; wherein the supported bimetallic catalyst includes a first catalyst component that is preferably non-metallocene, and a second catalyst component that includes a metallocene catalyst compound having at least one fluoride or fluorine containing leaving group, wherein the bimetallic catalyst is supported by an enhanced silica, dehydrated at a temperature of 800° C. or more in one embodiment.

CROSS-REFERENCE TO RELATED APPLICATION

The present application is a Divisional Application of, and claimspriority to U.S. Ser. No. 10/368,818 filed Feb. 18, 2003, now issued asU.S. Pat. No. 6,875,828, which claims priority to U.S. Ser. No.60/408,430 filed Sep. 4, 2002 and is herein incorporated by reference.

FIELD OF INVENTION

The present invention relates to bimodal polyolefin production, and moreparticularly, to bimodal polyolefins in producing films, wherein thebimodal polyolefin is produced in a single reactor using a bimetalliccatalyst in a desirable embodiment.

BACKGROUND

Bimodal polymers produced using two or more different catalysttypes—bimetallic catalysts—are of increasing interest, especially inproducing polyethylene and other polyolefins. See, for example, U.S.Pat. No. 5,525,678. However, problems exist in using these bimetalliccatalysts, especially in the gas phase. One problem is catalystactivity, which should be as high as possible in order to economize theprocess, as catalysts costs are significant.

One method of improving catalyst efficiency in gas phase processes is toimprove upon the catalyst used in the process. A promising class ofsingle-site catalysts for commercial use includes those wherein themetal center has at least one extractable fluorine (or fluorine “leavinggroup”). Disclosures of such catalysts include U.S. application Ser. No.20020032287; WO 97/07141; DE 43 32 009 A1; EP-A2 0 200 351; EP-A1 0 705849; E. F. Murphy, et al., Synthesis and spectroscopic characterizationof a series of substituted cyclopentadienyl Group 4 fluorides; crystalstructure of the acetylacetonato complex[(acac)₂(η⁵-C₅Me₅)Zr(μ-F)SnMe₃Cl], DALTON, 1983 (1996); A. Herzog, etal., Reactions of (η⁵-C ₅ Me ₅)ZrF ₃, (η⁵-C ₅ Me ₄ Et)ZrF ₃, (η⁵-C ₅ Me₅)HfF₃, and (η⁵-C ₅ Me ₅)TaF ₄ with AlMe ₃ , Structure of the FirstHafnium-Aluminum-Carbon Cluster, 15 ORGANOMETALLICS 909-917 (1996); F.Garbassi, et al., JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL 101 199-209(1995); and W. Kaminsky, et al., Fluorinated Half-Sandwich Complexes asCatalysts in Syndiospecific Styrene Polymerization, 30(25)MACROMOLECULES 7647-7650 (1997). Use of such single site catalystcomponents in a olefin polymerization system is desirable, especially ingas-phase polyethylene polymerization. It would be desirable to furtherimprove upon this system, especially for bimodal gas phasepolymerization processes. The present invention is directed towardssolving this and other problems.

SUMMARY

The present invention provides a method for bimodal polyolefinproduction, preferably using bimetallic catalysts, and polyolefins filmsmade from bimodal polyolefin compositions. At least one embodiment ofthe invention is directed to a process of producing a bimodal polyolefincomposition that includes contacting monomers with a supportedbimetallic catalyst composition for a time sufficient to form a bimodalpolyolefin composition; wherein the supported bimetallic catalystincludes a first catalyst component and a second catalyst component thatincludes a metallocene catalyst compound having at least one fluoride orfluorine containing leaving group.

Another specific embodiment of the invention is directed to a process ofproducing a bimodal polyolefin composition comprising contactingmonomers with a supported bimetallic catalyst composition for a timesufficient to form the bimodal polyolefin composition that includes ahigh molecular weight polyolefin component and a low molecular weightpolyolefin component; wherein the supported bimetallic catalyst includesa first catalyst component that includes a fluorinated metallocenerepresented by the formula Cp₂MF₂ wherein Cp is a substituted orunsubstituted cyclopentadienyl ring or derivative thereof, M is a Group4, 5, or 6 transition metal and a support material comprising silicadehydrated at a temperature of 800° C. or more.

Yet another specific embodiment of the invention is directed to aprocess of producing a bimodal polyolefin composition, includingproviding a particulate support material comprising silica; heating theparticulate support material to a temperature of 800° C. or more for atime sufficient to form a dehydrated support material includingdehydrated silica; combining the dehydrated support material with anon-polar hydrocarbon to provide a support slurry; providing a firstcatalyst component that is a non-metallocene catalyst; providing asecond catalyst component that includes a metallocene catalyst compoundhaving at least one fluoride or fluorine containing leaving group;combining the support slurry with the first and second catalystcomponents to form a supported bimetallic catalyst composition; andcontacting monomers with the bimetallic catalyst composition for a timesufficient to form a bimodal polyolefin composition having a density offrom 0.86 g/cm³ to 0.97 g/cm³, a molecular weight distribution of from 5to 80, a I₂ of from 0.01 dg/min to 50 dg/min, and a melt index ratio offrom 40 to 500.

In certain aspects, a film made from one or more of the bimodalpolyolefin compositions disclosed herein has a Dart Drop Impact F50Value of at least 100 [g] on 25.4 micron film and 75 [g] on 12.5 micronfilm.

In certain aspects, a film made from one or more of the bimodalpolyolefin compositions disclosed herein has an MD Tear value of atleast 0.4 g/micron on 25.4 micron film and at least 0.2 g/micron on 12.5micron film.

In certain aspects, a film made from one or more of the bimodalpolyolefin compositions disclosed herein has a TD Tear value of at least1.5 g/micron on 24.5 micron film and 1.0 g/micron on 12.5 micron film.

In particular embodiments, the support material useful in the process ofthe invention has been enhanced, in that it includes silica dehydratedat a temperature of 800° C. or more. In a more particular embodiment,the support material includes silica dehydrated at a temperature of 830°C. or more. In yet a more particular embodiment, the support materialincludes silica dehydrated at a temperature of 875° C. or more.

DETAILED DESCRIPTION

General Definitions

As used herein, in reference to Periodic Table “Groups” of Elements, the“new” numbering scheme for the Periodic Table Groups are used as in theCRC HANDBOOK OF CHEMISTRY AND PHYSICS (David R. Lide ed., CRC Press81^(st) ed. 2000).

As used herein, the phrase “catalyst system” includes at least one“catalyst component” and at least one “activator”, both of which aredescribed further herein. The catalyst system may also include othercomponents, such as supports, etc., and is not limited to the catalystcomponent and/or activator alone or in combination. The catalyst systemmay include any number of catalyst components in any combination asdescribed herein, as well as any activator in any combination asdescribed herein.

As used herein, the phrase “catalyst compound” includes any compoundthat, once appropriately activated, is capable of catalyzing thepolymerization or oligomerization of olefins, the catalyst compoundcomprising at least one Group 3 to Group 12 atom, and optionally atleast one leaving group bound thereto.

As used herein, the phrase “leaving group” refers to one or morechemical moieties bound to the metal center of the catalyst componentthat can be abstracted from the catalyst component by an activator, thusproducing the species active towards olefin polymerization oroligomerization. The activator is described further below.

As used herein, the term “fluorinated catalyst component” or “fluoridedcatalyst component” means a catalyst compound having at least onefluoride or fluorine containing leaving group, preferably a metalloceneor metallocene-type catalyst compound having at least one fluoride orfluorine containing leaving group.

As used herein, a “hydrocarbyl” includes aliphatic, cyclic, olefinic,acetylenic and aromatic radicals (i.e., hydrocarbon radicals) comprisinghydrogen and carbon that are deficient by one hydrogen. A“hydrocarbylene” is deficient by two hydrogens.

As used herein, an “alkyl” includes linear, branched and cyclic paraffinradicals that are deficient by one hydrogen. Thus, for example, a —CH₃group (“methyl”) and a CH₃CH₂— group (“ethyl”) are examples of alkyls.

As used herein, an “alkenyl” includes linear, branched and cyclic olefinradicals that are deficient by one hydrogen; alkynyl radicals includelinear, branched and cyclic acetylene radicals deficient by one hydrogenradical.

As used herein, “aryl” groups includes phenyl, naphthyl, pyridyl andother radicals whose molecules have the ring structure characteristic ofbenzene, naphthylene, phenanthrene, anthracene, etc. For example, a C₆H₅⁻ aromatic structure is an “phenyl”, a C₆H₄ ²⁻ aromatic structure is an“phenylene”. An “arylalkyl” group is an alkyl group having an aryl grouppendant therefrom; an “alkylaryl” is an aryl group having one or morealkyl groups pendant therefrom.

As used herein, an “alkylene” includes linear, branched and cyclichydrocarbon radicals deficient by two hydrogens. Thus, —CH₂—(“methylene”) and —CH₂CH₂— (“ethylene”) are examples of alkylene groups.Other groups deficient by two hydrogen radicals include “arylene” and“alkenylene”.

As used herein, the phrase “heteroatom” includes any atom other thancarbon and hydrogen that can be bound to carbon, and in one embodimentis selected from the group consisting of B, Al, Si, Ge, N, P, O, and S.A “heteroatom-containing group” is a hydrocarbon radical that contains aheteroatom and may contain one or more of the same or differentheteroatoms, and from 1 to 3 heteroatoms in a particular embodiment.Non-limiting examples of heteroatom-containing groups include radicalsof imines, amines, oxides, phosphines, ethers, ketones, oxoazolinesheterocyclics, oxazolines, thioethers, and the like.

As used herein, an “alkylcarboxylate”, “arylcarboxylate”, and“alkylarylcarboxylate” is an alkyl, aryl, and alkylaryl, respectively,that possesses a carboxyl group in any position. Examples includeC₆H₅CH₂C(O)O⁻, CH₃C(O)O⁻, etc.

As used herein, the term “substituted” means that the group followingthat term possesses at least one moiety in place of one or morehydrogens in any position, the moieties selected from such groups ashalogen radicals (esp., Cl, F, Br), hydroxyl groups, carbonyl groups,carboxyl groups, amine groups, phosphine groups, alkoxy groups, phenylgroups, naphthyl groups, C₁ to C₁₀ alkyl groups, C₂ to C₁₀ alkenylgroups, and combinations thereof. Examples of substituted alkyls andaryls includes, but are not limited to, acyl radicals, alkylaminoradicals, alkoxy radicals, aryloxy radicals, alkylthio radicals,dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonylradicals, carbomoyl radicals, alkyl- and dialkyl-carbamoyl radicals,acyloxy radicals, acylamino radicals, arylamino radicals, andcombinations thereof.

As used herein, structural formulas are employed as is commonlyunderstood in the chemical arts; lines (“

”) used to represent associations between a metal atom (“M”, Group 3 toGroup 12 atoms) and a ligand or ligand atom (e.g., cyclopentadienyl,nitrogen, oxygen, halogen ions, alkyl, etc.), as well as the phrases“associated with”, “bonded to” and “bonding”, are not limited torepresenting a certain type of chemical bond, as these lines and phrasesare meant to represent a “chemical bond”; a “chemical bond” defined asan attractive force between atoms that is strong enough to permit thecombined aggregate to function as a unit, or “compound”.

A certain stereochemistry for a given structure or part of a structureshould not be implied unless so stated for a given structure or apparentby use of commonly used bonding symbols such as by dashed lines and/orheavy lines.

Unless stated otherwise, no embodiment of the present invention isherein limited to the oxidation state of the metal atom “M” as definedbelow in the individual descriptions and examples that follow. Theligation of the metal atom “M” is such that the compounds describedherein are neutral, unless otherwise indicated.

As used herein, the term “bimodal,” when used to describe a polymer orpolymer composition (e.g., polyolefins such as polypropylene orpolyethylene, or other homopolymers, copolymers or terpolymers) means“bimodal molecular weight distribution,” which is understood as havingthe broadest definition persons in the pertinent art have given thatterm as reflected in printed publications and issued patents. Forexample, a single composition that includes polyolefins with at leastone identifiable high molecular weight distribution and polyolefins withat least one identifiable low molecular weight distribution isconsidered to be a “bimodal” polyolefin, as that term is used herein. Ina particular embodiment, other than having different molecular weights,the high molecular weight polyolefin and the low molecular weightpolyolefin are essentially the same type of polymer, for example,polypropylene or polyethylene.

As used herein, the term “productivity” means the weight of polymerproduced per weight of the catalyst used in the polymerization process(e.g., grams polymer/gram catalyst).

As used herein, the term “dehydrated” is understood as having thebroadest definition persons in the pertinent art have given that term indescribing catalyst support materials, for example, silica, as reflectedin printed publications and issued patents, and includes any material,for example, a support particle, from which a majority of thecontained/adsorbed water has been removed.

Gas-phase Polymerization Using Bimetallic Catalysts Comprising aFluorided Metallocene Catalyst Component

The present invention provides a process for producing a bimodalpolyolefin composition comprising: contacting olefin monomers with abimetallic catalyst composition to form a bimodal polyolefincomposition; wherein the bimetallic catalyst composition comprises: afirst catalyst component; and metallocene catalyst compound having atleast one fluoride or fluorine containing leaving group. In a particularembodiment, the bimetallic catalyst is supported. The bimetalliccatalyst, each of its components, and the method of polymerization areset out in greater detail below.

In one aspect of the invention, the method of making bimodal polymers ischaracterized in that the monomers are contacted with the bimetalliccatalyst in a single reactor vessel and form the bimodal polyolefincomposition in the same reactor vessel.

The present invention also provides a bimodal film compositioncomprising a polyolefin having a density of from 0.86 g/cm³ to 0.97g/cm³, a molecular weight distribution of from 5 to 80, a melt index offrom 0.01 dg/min to 50 dg/min, and a melt index ratio of from 40 to 500.The film composition, or film, is formed from the bimetallic catalyst ofthe invention, and has certain desirable features as set out furtherbelow.

Bimetallic Catalyst

As used herein, the term “bimetallic catalyst” or “bimetallic catalystsystem” refers to two or more catalyst components used in combinationwith at least one activator, and optionally a support material, that isuseful in polymerizing olefins. The “supported bimetallic catalyst” or“supported bimetallic catalyst composition” refers the bimetalliccatalyst system as used in combination with a support material, whereinone or more of the components that make up the bimetallic catalystsystem may be bound to the support. In a particular embodiment, thebimetallic catalyst of the invention includes two catalyst components.In a more particular embodiment, the bimetallic catalyst componentincludes a “first catalyst component” and a “second catalyst component”.

As used herein, the term “first catalyst component” refers to anycatalyst component other than the second catalyst component. Preferably,the first catalyst component is a non-metallocene catalyst component,examples of which include titanium or vanadium based Ziegler-Nattacatalysts compounds as described further herein.

As used herein, the term “non-metallocene compound” refers any catalystthat is neither a metallocene nor one of the metallocene-type catalystcompounds identified below.

As used herein, the term “second catalyst component” refers to anycatalyst that is different from a first catalyst component, ametallocene catalyst component in a particular embodiment. In aparticular embodiment, the second catalyst component includes afluorided metallocene component which comprises at least one fluorideion leaving group or fluorine containing group.

Certain embodiments of the present invention involve contacting monomerswith the bimetallic catalyst component. In a particular embodiment, eachdifferent catalyst compound that comprises the bimetallic catalystresides, or is supported on a single type of support such that, onaverage, each particle of support material includes both the first andsecond catalyst components. In another embodiment, the first catalystcomponent is supported separately from the second catalyst componentsuch that on average any given particle of support material comprisesonly the first or the second catalyst component. In this laterembodiment, each supported catalyst may be introduced into thepolymerization reactor sequentially in any order, alternately in parts,or simultaneously.

In a particular embodiment, the first catalyst component includes atitanium non-metallocene catalyst component, from which a highermolecular weight resin (e.g., >ca 100,000 amu) can be produced. In aparticular embodiment, the second catalyst component includes ametallocene component, from which a lower molecular weight resin (e.g.,<ca 100,000 amu) can be produced. Accordingly, polymerization in thepresence of the first and second catalyst components provides a bimodalpolyolefin composition that includes a low molecular weight componentand a high molecular weight component. The two catalyst componentsreside on a single support particle in a particular embodiment, and theycan be affixed to the support in a variety of ways.

In one embodiment, an “enhanced silica” is prepared as described hereinand constitutes the support; the first catalyst component is anon-metallocene compound that is first combined with the enhancedsilica, to provide a supported non-metallocene composition; thesupported non-metallocene composition is combined with the secondcatalyst component, for example, a fluorided metallocene (a metallocenehaving at least one fluorine ion leaving group), resulting in afluorinated bimetallic catalyst composition having enhanced productivitywhen used in production of a bimodal polyolefin composition.

Various methods of affixing two different catalyst components (albeit adifferent combination of catalysts) to a support can be used. Ingeneral, one procedure for preparing a supported bimetallic catalyst caninclude providing a supported first catalyst component, contacting aslurry that includes the first catalyst component in a non-polarhydrocarbon with a solution that includes the second catalyst component,which may also include an activator, and drying the resulting productthat includes the first and second catalyst components and recovering abimetallic catalyst composition.

First Catalyst Component

As noted above, the bimetallic catalyst composition includes a firstcatalyst component, which is (or includes) a non-metallocene compound.However, it is contemplated that for certain applications the firstcatalyst component may alternatively be a metallocene compound, or evenone of the metallocene-type catalyst compounds identified below that isdifferent in structure from the second catalyst component as describedherein. In a particular embodiment, the first catalyst component is aZiegler-Natta catalyst compound. Ziegler-Natta catalyst components arewell known in the art and described by, for example, in ZIEGLERCATALYSTS 363-386 (G. Fink, R. Mulhaupt and H. H. Brintzinger, eds.,Springer-Verlag 1995). Examples of such catalysts include thosecomprising TiCl₄ and other such transition metal oxides and chlorides.

The first catalyst component is combined with a support material in oneembodiment, either with or without the second catalyst component. Thefirst catalyst component can be combined with, placed on or otherwiseaffixed to a support in a variety of ways. In one of those ways, aslurry of the support in a suitable non-polar hydrocarbon diluent iscontacted with an organomagnesium compound, which then dissolves in thenon-polar hydrocarbon diluent of the slurry to form a solution fromwhich the organomagnesium compound is then deposited onto the carrier.The organomagnesium compound can be represented by the formula RMgR′,where R′ and R are the same or different C₂-C₁₂ alkyl groups, or C₄-C₁₀alkyl groups, or C₄-C₈ alkyl groups. In at least one specificembodiment, the organomagnesium compound is dibutyl magnesium. In oneembodiment, the amount of organomagnesium compound included in thesilica slurry is only that which will be deposited, physically orchemically, onto the support, for example, being bound to the hydoxylgroups on the support, and no more than that amount, since any excessorganomagnesium compound may cause undesirable side reactions. Routineexperimentation can be used to determine the optimum amount oforganomagnesium compound. For example, the organomagnesium compound canbe added to the slurry while stirring the slurry, until theorganomagnesium compound is detected in the support solvent.Alternatively, the organomagnesium compound can be added in excess ofthe amount that is deposited onto the support, in which case anyundeposited excess amount can be removed by filtration and washing. Theamount of organomagnesium compound (moles) based on the amount ofdehydrated silica (grams) generally range from 0.2 mmol/g to 2 mmol/g inone embodiment.

Optionally, the organomagnesium compound-treated slurry is contactedwith an electron donor, such as tetraethylorthosiloxane (TEOS) or anorganic alcohol R″OH, where R″ is a C₁-C₁₂ alkyl group, or a C₁ to C₈alkyl group, or a C₂ to C₄ alkyl group. In a particular embodiment, R″OHis n-butanol. The amount of alcohol used in an amount effective toprovide an R″OH:Mg mol/mol ratio of from 0.2 to 1.5, or from 0.4 to 1.2,or from 0.6 to 1.1, or from 0.9 to 1.0.

The organomagnesium and alcohol-treated slurry is contacted with anon-metallocene transition metal compound. Suitable non-metallocenetransition metal compounds are compounds of Group 4 and 5 metals thatare soluble in the non-polar hydrocarbon used to form the silica slurry.Suitable non-metallocene transition metal compounds include, forexample, titanium and vanadium halides, oxyhalides or alkoxyhalides,such as titanium tetrachloride (TiCl₄), vanadium tetrachloride (VCl₄)and vanadium oxytrichloride (VOCl₃), and titanium and vanadiumalkoxides, wherein the alkoxide moiety has a branched or unbranchedalkyl group of 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms.Mixtures of such transition metal compounds may also be used. The amountof non-metallocene transition metal compound used is sufficient to givea transition metal to magnesium mol/mol ratio of from 0.3 to 1.5, orfrom 0.5 to 0.8. The diluent can then be removed in a conventionalmanner, such as by evaporation or filtering, to obtain the dry,supported first catalyst component.

The first and second catalyst components may be contacted with thesupport in any order. In a particular embodiment of the invention, thefirst catalyst component is reacted first with the support as describedabove, followed by contacting this supported first catalyst componentwith a second catalyst component.

Process for Making a Fluorinated Catalyst Compound

Embodiments of the invention include a process of producing afluorinated catalyst compound, and in particular, a fluoridedmetallocene catalyst component. The fluorided metallocene itself isdescribed in more detail below. The fluorided metallocene catalystcomponent can be (or include) any fluorided metallocene catalystcomponent, but is preferably a fluorided metallocene catalyst component.The fluorided metallocene catalyst component can be, for example, anyone of the catalysts described in greater detail below, or the “secondcatalyst component” of the bimodal catalyst. The fluorided catalystcompound is preferably a metallocene type compound having the generalformula (Cp(R)_(p))_(m)MX_(n)F_(r) (which can include, for example, apartially fluorinated metallocene), wherein Cp is a cyclopentadienylligand or ligand isolobal to cyclopentadienyl (as described furtherbelow) that can be substituted in any position by a group R as set outbelow, M is a Group 4, 5, or 6 transition metal in a particularembodiment, X is an anionic ligand such as a halogen, carboxylate,acetylacetonate, alkoxide, hydroxide, or oxide; p is an integer from 0to 10, m is an integer from 1 to 3, n is an integer from 0 to 3, and ris an integer from 1 to 3.

The process includes contacting a metallocene catalyst compound with afluoriding agent, and more particularly, a fluorinated inorganic salt,for a time sufficient to form the fluorided metallocene catalystcompound. The metallocene catalyst compound preferably has the samegeneral formula as the desired fluorinated metallocene compound, withthe exception that the one or more leaving groups X are an anionicligand (e.g., chlorine or bromine) rather than fluorine. The metallocenecompound that is contacted with the fluoriding agent may be commerciallyavailable, or may be prepared by methods known to one skilled in theart.

The metallocene compound may include a cyclopentadienyl ligand or ligandisolobal to Cp, either substituted or unsubstituted. The amount ofsubstitution on Cp may affect the yield of the fluorinated metallocenecompound. Therefore, at least one Cp of the metallocene is substitutedin one embodiment, and two Cps are substituted in another embodiment,wherein the metallocene is a sandwich metallocene as set out below. In aparticular embodiment, the substituent group (R) is not an aryl groupsuch as phenyl, indenyl or fluorenyl. In at least certain embodiments,it has been discovered that benzene substituent groups correspond toreduced product yields. For example, when R is indenyl, the productyield may be as low as zero. Preferably, the substituent groups includehydrocarbyl groups. In a preferred embodiment, alkyl substitutionresults in surprisingly high yields, for example, 95% or more.

In one embodiment, the fluoriding agent is a fluorinated inorganic saltor combination of salts described by the general formula (a):[α]_(a)[β]_(b),  (a)

-   wherein α is a cationic species selected from the group consisting    of Group 1 and 2 cations; anilinium and substituted versions    thereof; and NH₄ ⁺, NH₃R, NH₂R₂, and NHR₃ ⁺ wherein R is selected    from the group consisting of hydride, chloride, C₁ to C₁₀ alkyl and    C₆ to C₁₂ aryls;-   β is an anionic species selected from the group consisting of    fluorine ions and compounds comprising fluorine and one or more    elements selected from the group consisting of hydrogen, silicon,    carbon, phosphorous, oxygen, aluminum and boron; and-   a and b are integers from 1 to 10.

In a particular embodiment, the fluorinated inorganic salt is a compoundcharacterized in that it is capable of generating fluoride ions whencontacted with water or other protic diluent. Non-limiting examples ofthe fluorinated inorganic salt include (NH₄)₃AlF₆, NH₄HF₂, NaF, KF,NH₄F, (NH₄)₂SiF₆ and combinations thereof.

The fluorinated inorganic salt compound may include a fluorinatedinorganic salt mixture. The fluorinated inorganic salt compound ispreferably soluble or partially soluble in a diluent. Therefore, themixture may include the fluorinated inorganic salt and a diluent, thatis, the fluorinated inorganic salt may be dissolved in a diluent priorto contacting the metallocene catalyst compound. The diluent may includean organic diluent. In a particular embodiment, the diluent is water orwater in combination with some other polar diluent that is miscible withwater (e.g., ethers, ketones, aldehydes, etc). In another embodiment,the diluent is any desirable protic medium. In a particular embodiment,the fluorinated inorganic salt is combined with a diluent that is atleast 50 wt % water, and at least 60 wt % water in another embodiment,and at least 70 wt % water in yet another embodiment, and at least 80 wt% water in yet another embodiment, and at least 90 wt % in a particularembodiment, and at least 99 wt % water in a more particular embodiment.

The metallocene compound that is contacted with the fluoriding agent maybe initially charged in an inert or non-protic diluent. The inertdiluent may include one of, or a mixture of, aliphatic and aromatichydrocarbons or a halogenated solvent. Suitable hydrocarbons includesubstituted and unsubstituted aliphatic hydrocarbons and substituted andunsubstituted aromatic hydrocarbons. In a particular embodiment, theinert diluent is selected from the group consisting of C₃ to C₃₀hydrocarbons and C₁ to C₁₀ halogenated hydrocarbons and mixtures thereofin a particular embodiment. Non-limiting examples of suitable inertdiluents include hexane, heptane, octane, decane, toluene, xylene,dichloromethane, dichloroethane, chloroform and 1-chlorobutane.

In a particular embodiment of the method of fluoriding metallocenesdescribed herein, the fluorinated inorganic salt combined with a proticdiluent is reacted with the metallocene combined with an inert diluent.In a more particular embodiment, the fluorinated inorganic salt in atleast 50% water is combined with the metallocene to be fluorideddissolved/suspended in a hydrocarbon or halogenated hydrocarbon diluent.The combined reactants may form two or more phases in contact with oneanother. The fluoriding reaction then takes place under desirable mixingand temperature conditions.

In embodiments of the fluoriding step wherein the fluoriding agent isimmiscible or only partially miscible with the diluent, it is within thescope of the invention to use a reagent that will assist the transportof the fluoriding agent to the alkylated catalyst component or thediluent phase in which the alkylated catalyst component exists, orassist in the reaction between the fluoriding agent and alkylatedcatalyst component. Such reagents—phase-transfer catalysts—are known inthe art and are used in reactions wherein, for example, an aqueous orpolar diluent phase is in contact with a non-polar or hydrocarbondiluent phase, and the reactants are separated as such. Non-limitingexamples of such phase-transfer catalysts include quaternary ammoniumsalts (e.g., quaternary ammonium bisulfate), crown ethers, and otherscommon in the art.

Depending on the desired degree of substitution, the ratio of fluorine(of the fluoriding agent) to metallocene combined to react is from 1equivalent to 20 equivalents in one embodiment, and from 2 to 10equivalents in another embodiment, and from 2 to 8 equivalents in yetanother embodiment, and from 2 to 5 equivalents in yet anotherembodiment, wherein a desirable range comprises any combination of anyupper limit with any lower limit. While excess fluorinated inorganicsalt may not be detrimental, the molar ratio of the reactants ispreferably determined by the number of anionic ligands to be substitutedin the metallocene compound, that is, the number of anionic ligands tobe replace by fluorine or fluoride atoms. In a particular embodiment,the number of anionic ligands to be substituted is 2.

Stated another way, the desired amount of fluoriding agent, based on theequivalents of fluorine in the fluoriding agent, that is combined withthe metallocene catalyst compound ranges from 1, or 2, or 3, or 4, or 5to 6, or 7, or 8, or 10, or 12, or 14 or 15 or 18 or 20, wherein adesirable range comprises any combination of any upper limit with anylower limit described herein. In another embodiment, the desired amountof fluoriding agent, based on the equivalents of fluoriding agent as awhole, ranges from 1, or 2, or 3, or 4 to 5 or 6, or 7, or 8, or 9, or10, wherein a desirable range comprises any combination of any upperlimit with any lower limit described herein.

The fluorinated inorganic salt may be reacted with the metallocenecompound by vigorously stirring the compounds. The reaction may occur atany temperature that affords the desired mono-, di- or trifluoridedmetallocene, including temperatures of from −80° C. to 120° C. in oneembodiment, and from 0 to 100° C. in a more particular embodiment, andfrom 10 to 60° C. in yet a more particular embodiment, and from 15 to40° C. in yet a more particular embodiment. At those temperatures,reaction times of 0.05 hour to 8 hours are sufficient to form afluorinated metallocene compound, but routine experimentation may bedesirable to arrive at an optimum temperature. Generally, the reactiontime is dependent upon the amount of reactants reacted. In oneembodiment, the reaction time is from 0.1 hour to 3 hours.

The diluent, along with reaction by-products, can be removed from themixture in a conventional manner, such as by evaporation or filtering,to obtain the dry, fluorinated metallocene compound. For example, thefluorided metallocene may be dried in the presence of magnesium sulfate.The filtrate, which contains the fluorinated metallocene compound inhigh purity and yield, can without further processing be directly usedin the polymerization of olefins if the solvent is a hydrocarbon.

Contacting the metallocene compound with the fluorinated inorganic salt,an aqueous fluorinated inorganic salt, results in a product yield of 50%or more in a particular embodiment. The product yield is 80% or more inyet a more particular embodiment. The product yield is 90% or more inyet a more particular embodiment. Unexpectedly, contacting themetallocene compound with the aqueous solution of fluorinated inorganicsalt results in a fluorided metallocene compound having highproductivities.

Fluorided Metallocene Catalyst Component

The bimetallic catalyst system useful in the present invention includesa second catalyst component that comprises at least one fluoridedmetallocene catalyst component as described herein. Metallocene catalystcompounds are generally described throughout in, for example, 1 & 2METALLOCENE-BASED POLYOLEFINS (John Scheirs & W. Kaminsky eds., JohnWiley & Sons, Ltd. 2000); G. G. Hlatky in 181 COORDINATION CHEM. REV.243-296 (1999) and in particular, for use in the synthesis ofpolyethylene in 1 METALLOCENE-BASED POLYOLEFINS 261-377 (2000). Themetallocene catalyst compounds as described herein include “halfsandwich” and “full sandwich” compounds having one or more Cp ligands(cyclopentadienyl and ligands isolobal to cyclopentadienyl) bound to atleast one Group 3 to Group 12 metal atom, and one or more leavinggroup(s) bound to the at least one metal atom. Hereinafter, thesecompounds will be referred to as “metallocenes” or “metallocene catalystcomponents”. The fluorided metallocene components are those wherein atleast one leaving group bound to M is a fluoride ion or afluorine-containing group. The metallocene catalyst component issupported on a support material in a particular embodiment as describedfurther below, and may be supported with or without the first catalystcomponent, with the first catalyst component in a particular embodiment.

The Cp ligands are typically π-bonded and/or fused ring(s) or ringsystems. The ring(s) or ring system(s) typically comprise atoms selectedfrom the group consisting of Groups 13 to 16 atoms, and moreparticularly, the atoms that make up the Cp ligands are selected fromthe group consisting of carbon, nitrogen, oxygen, silicon, sulfur,phosphorous, germanium, boron and aluminum and combinations thereof,wherein carbon makes up at least 50% of the ring members. Even moreparticularly, the Cp ligand(s) are selected from the group consisting ofsubstituted and unsubstituted cyclopentadienyl ligands and ligandsisolobal to cyclopentadienyl, non-limiting examples of which includecyclopentadienyl, indenyl, fluorenyl and other structures. Furthernon-limiting examples of such ligands include cyclopentadienyl,cyclopentaphenanthreneyl, indenyl, benzindenyl, fluorenyl,octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene,phenanthrindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl,8-H-cyclopent[a]acenaphthylenyl, 7H-dibenzofluorenyl,indeno[1,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl,hydrogenated versions thereof (e.g., 4,5,6,7-tetrahydroindenyl, or“H₄Ind”), substituted versions thereof, and heterocyclic versionsthereof. In a particular embodiment, the metallocenes useful in thepresent invention are selected from those including one or two, two in amore particular embodiment, of the same or different Cp rings selectedfrom the group consisting of cyclopentadienyl, indenyl, fluorenyl,tetrahydroindenyl, and substituted versions thereof.

The metal atom “M” of the metallocene catalyst compound, as describedthroughout the specification and claims, may be selected from the groupconsisting of Groups 3 through 12 atoms and lanthanide Group atoms inone embodiment; and selected from the group consisting of Groups 3through 10 atoms in a more particular embodiment, and selected from thegroup consisting of Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co,Rh, Ir, and Ni in yet a more particular embodiment; and selected fromthe group consisting of Groups 4, 5 and 6 atoms in yet a more particularembodiment, and a Ti, Zr, Hf atoms in yet a more particular embodiment,and Zr in yet a more particular embodiment. The oxidation state of themetal atom “M” may range from 0 to +7 in one embodiment; and in a moreparticular embodiment, is +1, +2, +3, +4 or +5; and in yet a moreparticular embodiment is +2, +3 or +4. The groups bound the metal atom“M” are such that the compounds described below in the formulas andstructures are electrically neutral, unless otherwise indicated. The Cpligand(s) form at least one chemical bond with the metal atom M to formthe “metallocene catalyst compound”. The Cp ligands are distinct fromthe leaving groups bound to the catalyst compound in that they are nothighly susceptible to substitution/abstraction reactions.

In one aspect of the invention, the one or more metallocene catalystcomponents of the invention are represented by the formula (I):Cp^(A)Cp^(B)MX_(n)  (I)wherein M is as described above; each X is chemically bonded to M; eachCp group is chemically bonded to M; and n is an integer from 0 to 4, andeither 1 or 2 in a particular embodiment.

The ligands represented by Cp^(A) and Cp^(B) in formula (I) may be thesame or different cyclopentadienyl ligands or ligands isolobal tocyclopentadienyl, either or both of which may contain heteroatoms andeither or both of which may be substituted by a group R. In oneembodiment, Cp^(A) and Cp^(B) are independently selected from the groupconsisting of the group consisting of cyclopentadienyl, indenyl,tetrahydroindenyl, fluorenyl, and substituted derivatives of each.

Independently, each Cp^(A) and Cp^(B) of formula (I) may beunsubstituted or substituted with any one or combination of substituentgroups R. Non-limiting examples of substituent groups R as used instructure (I) as well as ring substituents in structures (Va-d) includegroups selected from the group consisting of hydrogen radicals, alkyls,alkenyls, alkynyls, cycloalkyls, aryls, acyls, aroyls, alkoxys,aryloxys, alkylthiols, dialkylamines, alkylamidos, alkoxycarbonyls,aryloxycarbonyls, carbomoyls, alkyl- and dialkyl-carbamoyls, acyloxys,acylaminos, aroylaminos, and combinations thereof.

More particular non-limiting examples of alkyl substituents R associatedwith formula (I) through (V) include methyl, ethyl, propyl, butyl,pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl,and tert-butylphenyl groups and the like, including all their isomers,for example tertiary-butyl, isopropyl, and the like. Other possibleradicals include substituted alkyls and aryls such as, for example,fluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl,chlorobenzyl and hydrocarbyl substituted organometalloid radicalsincluding trimethylsilyl, trimethylgermyl, methyldiethylsilyl and thelike; and halocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstituted boron radicalsincluding dimethylboron for example; and disubstituted Group 15 radicalsincluding dimethylamine, dimethylphosphine, diphenylamine,methylphenylphosphine, Group 16 radicals including methoxy, ethoxy,propoxy, phenoxy, methylsulfide and ethylsulfide. Other substituents Rinclude olefins such as but not limited to olefinically unsaturatedsubstituents including vinyl-terminated ligands, for example 3-butenyl,2-propenyl, 5-hexenyl and the like. In one embodiment, at least two Rgroups, two adjacent R groups in one embodiment, are joined to form aring structure having from 3 to 30 atoms selected from the groupconsisting of carbon, nitrogen, oxygen, phosphorous, silicon, germanium,aluminum, boron and combinations thereof. Also, a substituent group Rgroup such as 1-butanyl may form a bonding association to the element M.

At least one X in the formula (I) above and for the formulas/structures(II) through (V) below is independently selected from the groupconsisting of fluoride ions, fluorinated C₆ to C₂₄ aryls, C₇ to C₂₅alkylaryls and fluorinated C₁ to C₁₂ alkyls, wherein “fluorinated” meansat least one, and up to 100% of the hydrogen atoms of the group arereplaced by fluorine atoms, and from 50 to 100% of the hydrogen atoms ina particular embodiment; selected independently from fluoride ions,methyl, ethyl, propyl, phenyl, methylphenyl, dimethylphenyl,trimethylphenyl, fluoromethyls (mono-, di- and trifluoromethyls) andfluorophenyls (mono-, di-, tri-, tetra- and pentafluorophenyls) in yet amore particular embodiment; and are fluoride ions in yet a moreparticular embodiment. In a particular embodiment, all X groups on themetallocene are fluorine or fluorine containing groups as described, andin yet a more particular embodiment, all of the X groups on themetallocene useful in the invention are fluorine ions.

Non-limiting examples of other X groups include alkyls, amines,phosphines, ethers, carboxylates, dienes, hydrocarbon radicals havingfrom 1 to 20 carbon atoms; fluorinated hydrocarbon radicals (e.g., —C₆F₅(pentafluorophenyl)), fluorinated alkylcarboxylates (e.g., CF₃C(O)O⁻),hydrides and halogen ions and combinations thereof. Other examples of Xligands include alkyl groups such as cyclobutyl, cyclohexyl, methyl,heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene,methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide),dimethylamide, dimethylphosphide radicals and the like. In oneembodiment, two or more X's form a part of a fused ring or ring system.

In another aspect of the invention, the metallocene catalyst componentincludes those of formula (I) where Cp^(A) and Cp^(B) are bridged toeach other by at least one bridging group, (A), such that the structureis represented by formula (II):Cp^(A)(A)Cp^(B)MX_(n)  (II)

These bridged compounds represented by formula (II) are known as“bridged metallocenes”. Cp^(A), Cp^(B), M, X and n in structure (II) areas defined above for formula (I); and wherein each Cp ligand ischemically bonded to M, and (A) is chemically bonded to each Cp.Non-limiting examples of bridging group (A) include divalent hydrocarbongroups containing at least one Group 13 to 16 atom, such as but notlimited to at least one of a carbon, oxygen, nitrogen, silicon,aluminum, boron, germanium and tin atom and combinations thereof;wherein the heteroatom may also be C₁ to C₁₂ alkyl or aryl substitutedto satisfy neutral valency. The bridging group (A) may also containsubstituent groups R as defined above (for formula (I)) includinghalogen radicals and iron. More particular non-limiting examples ofbridging group (A) are represented by C₁ to C₆ alkylenes, substituted C₁to C₆ alkylenes, oxygen, sulfur, R′₂C═, R′₂Si═, —Si(R′)₂Si(R′₂)—,R′₂Ge═, R′P═ (wherein “═” represents two chemical bonds), where R′ isindependently selected from the group consisting of hydride,hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, hydrocarbyl-substituted organometalloid,halocarbyl-substituted organometalloid, disubstituted boron,disubstituted Group 15 atoms, substituted Group 16 atoms, and halogenradical; and wherein two or more R′ may be joined to form a ring or ringsystem. In one embodiment, the bridged metallocene catalyst component offormula (II) has two or more bridging groups (A).

Other non-limiting examples of bridging group (A) include methylene,ethylene, ethylidene, propylidene, isopropylidene, diphenylmethylene,1,2-dimethylethylene, 1,2-diphenylethylene, 1,1,2,2-tetramethylethylene,dimethylsilyl, diethylsilyl, methyl-ethylsilyl,trifluoromethylbutylsilyl, bis(trifluoromethyl)silyl, di(n-butyl)silyl,di(n-propyl)silyl, di(i-propyl)silyl, di(n-hexyl)silyl,dicyclohexylsilyl, diphenylsilyl, cyclohexylphenylsilyl,t-butylcyclohexylsilyl, di(t-butylphenyl)silyl, di(p-tolyl)silyl and thecorresponding moieties wherein the Si atom is replaced by a Ge or a Catom; dimethylsilyl, diethylsilyl, dimethylgermyl and diethylgermyl.

In another embodiment, bridging group (A) may also be cyclic,comprising, for example 4 to 10, 5 to 7 ring members in a moreparticular embodiment. The ring members may be selected from theelements mentioned above, from one or more of B, C, Si, Ge, N and O in aparticular embodiment. Non-limiting examples of ring structures whichmay be present as or part of the bridging moiety are cyclobutylidene,cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene andthe corresponding rings where one or two carbon atoms are replaced by atleast one of Si, Ge, N and O, in particular, Si and Ge. The bondingarrangement between the ring and the Cp groups may be either cis-,trans-, or a combination.

The cyclic bridging groups (A) may be saturated or unsaturated and/orcarry one or more substituents and/or be fused to one or more other ringstructures. If present, the one or more substituents are selected fromthe group consisting of hydrocarbyl (e.g., alkyl such as methyl) andhalogen (e.g., F, Cl) in one embodiment. The one or more Cp groups whichthe above cyclic bridging moieties may optionally be fused to may besaturated or unsaturated and are selected from the group consisting ofthose having 4 to 10, more particularly 5, 6 or 7 ring members (selectedfrom the group consisting of C, N, O and S in a particular embodiment)such as, for example, cyclopentyl, cyclohexyl and phenyl. Moreover,these ring structures may themselves be fused such as, for example, inthe case of a naphthyl group. Moreover, these (optionally fused) ringstructures may carry one or more substituents. Illustrative,non-limiting examples of these substituents are hydrocarbyl(particularly alkyl) groups and halogen atoms.

The ligands Cp^(A) and Cp^(B) of formulae (I) and (II) are differentfrom each other in one embodiment, and the same in another embodiment.

In yet another aspect of the invention, the metallocene catalystcomponents include bridged mono-ligand metallocene compounds (e.g., monocyclopentadienyl catalyst components). In this embodiment, the at leastone metallocene catalyst component is a bridged “half-sandwich”metallocene represented by the formula (III):Cp^(A)(A)QMX_(n)  (III)wherein Cp^(A) is defined above and is bound to M; (A) is a bridginggroup bonded to Q and Cp^(A); and wherein an atom from the Q group isbonded to M; and n is an integer 0, 1 or 2. In formula (III) above,Cp^(A), (A) and Q may form a fused ring system. The X groups and n offormula (III) are as defined above in formula (I) and (II). In oneembodiment, Cp^(A) is selected from the group consisting ofcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, substitutedversions thereof, and combinations thereof.

In formula (III), Q is a heteroatom-containing ligand in which thebonding atom (the atom that is bonded with the metal M) is selected fromthe group consisting of Group 15 atoms and Group 16 atoms in oneembodiment, and selected from the group consisting of nitrogen,phosphorus, oxygen or sulfur atom in a more particular embodiment, andnitrogen and oxygen in yet a more particular embodiment. Non-limitingexamples of Q groups include alkylamines, arylamines, mercaptocompounds, ethoxy compounds, carboxylates (e.g., pivalate), carbamates,azenyl, azulene, pentalene, phosphoyl, phosphinimine, pyrrolyl,pyrozolyl, carbazolyl, borabenzene other compounds comprising Group 15and Group 16 atoms capable of bonding with M.

In yet another aspect of the invention, the at least one metallocenecatalyst component is an unbridged “half sandwich” metallocenerepresented by the formula (IVa):Cp^(A)MQ_(q)X_(n)  (IVa)wherein Cp^(A) is defined as for the Cp groups in (I) and is a ligandthat is bonded to M; each Q is independently bonded to M; X is a leavinggroup as described above in (I); n ranges from 0 to 3, and is 0 or 3 inone embodiment; q ranges from 0 to 3, and is 0 or 3 in one embodiment.In one embodiment, CPA is selected from the group consisting ofcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, substitutedversion thereof, and combinations thereof.

In formula (IVa), Q is selected from the group consisting of ROO⁻, RO—,R(O)—, —NR—, —CR₂—, —S—, —NR₂, —CR₃, —SR, —SiR₃, —PR₂, —H, andsubstituted and unsubstituted aryl groups, wherein R is selected fromthe group consisting of C₁ to C₆ alkyls, C₆ to C₁₂ aryls, C₁ to C₆alkylamines, C₆ to C₁₂ alkylarylamines, C₁ to C₆ alkoxys, C₆ to C₁₂aryloxys, and the like. Non-limiting examples of Q include C₁ to C₁₂carbamates, C₁ to C₁₂ carboxylates (e.g., pivalate), C₂ to C₂₀ allyls,and C₂ to C₂₀ heteroallyl moieties.

Described another way, the “half sandwich” metallocenes above can bedescribed as in formula (IVb), such as described in, for example, U.S.Pat. No. 6,069,213:Cp^(A)M(Q₂GZ)X_(n) orT(Cp^(A)M(Q₂GZ)X_(n))_(m)  (IVb)

-   wherein M, Cp^(A), X and n are as defined above;-   Q₂GZ forms a polydentate ligand unit (e.g., pivalate), wherein at    least one of the Q groups form a bond with M, and is defined such    that each Q is independently selected from the group consisting of    —O—, —NR—, —CR₂— and —S—; G is either carbon or silicon; and Z is    selected from the group consisting of R, —OR, —NR₂, —CR₃, —SR,    —SiR₃, —PR₂, and hydride, providing that when Q is —NR—, then Z is    selected from the group consisting of —OR, —NR₂, —SR, —SiR₃, —PR₂;    and provided that neutral valency for Q is satisfied by Z; and    wherein each R is independently selected from the group consisting    of C₁ to C₁₀ heteroatom containing groups, C₁ to C₁₀ alkyls, C₆ to    C₁₂ aryls, C₆ to C₁₂ alkylaryls, C₁ to C₁₀ alkoxys, and C₆ to C₁₂    aryloxys;-   n is 1 or 2 in a particular embodiment; and-   T is a bridging group selected from the group consisting of C₁ to    C₁₀ alkylenes, C₆ to C₁₂ arylenes and C₁ to C₁₀ heteroatom    containing groups, and C₆ to C₁₂ heterocyclic groups; wherein each T    group bridges adjacent “Cp^(A)M(Q₂GZ)X_(n)” groups, and is    chemically bonded to the Cp^(A) groups.-   m is an integer from 1 to 7; m is an integer from 2 to 6 in a more    particular embodiment.

In another aspect of the invention, the at least one fluoridedmetallocene catalyst component can be described more particularly instructures (Va), (Vb), (Vc) and (Vd):

-   wherein in structures (Va) to (Vd) M is selected from the group    consisting of Group 3 to Group 12 atoms, and selected from the group    consisting of Group 3 to Group 10 atoms in a more particular    embodiment, and selected from the group consisting of Group 3 to    Group 6 atoms in yet a more particular embodiment, and selected from    the group consisting of Group 4 atoms in yet a more particular    embodiment, and selected from the group consisting of Zr and Hf in    yet a more particular embodiment; and is Zr in yet a more particular    embodiment;-   wherein Q in (Va-i) and (Va-ii) is selected from the group    consisting of halogen ions, alkyls, alkylenes, aryls, arylenes,    alkoxys, aryloxys, amines, alkylamines, phosphines, alkylphosphines,    substituted alkyls, substituted aryls, substituted alkoxys,    substituted aryloxys, substituted amines, substituted alkylamines,    substituted phosphines, substituted alkylphosphines, carbamates,    heteroallyls, carboxylates (non-limiting examples of suitable    carbamates and carboxylates include trimethylacetate,    trimethylacetate, methylacetate, p-toluate, benzoate,    diethylcarbamate, and dimethylcarbamate), fluorinated alkyls,    fluorinated aryls, and fluorinated alkylcarboxylates;-   q is an integer ranging from 1 to 3;-   wherein each R* is independently: selected from the group consisting    of hydrocarbyls and heteroatom-containing hydrocarbyls in one    embodiment; and selected from the group consisting of alkylenes,    substituted alkylenes and heteroatom-containing hydrocarbyls in    another embodiment; and selected from the group consisting of C₁ to    C₁₂ alkylenes, C₁ to C₁₂ substituted alkylenes, and C₁ to C₁₂    heteroatom-containing hydrocarbons in a more particular embodiment;    and selected from the group consisting of C₁ to C₄ alkylenes in yet    a more particular embodiment; and wherein both R* groups are    identical in another embodiment in structures (Vb-d);-   A is as described above for (A) in structure (II), and more    particularly, selected from the group consisting of —O—, —S—, —SO₂—,    —NR—, ═SiR₂, ═GeR₂, ═SnR₂, —R₂SiSiR₂—, RP═, C₁ to C₁₂ alkylenes,    substituted C₁ to C₁₂ alkylenes, divalent C₄ to C₁₂ cyclic    hydrocarbons and substituted and unsubstituted aryl groups in one    embodiment; and selected from the group consisting of C₅ to C₈    cyclic hydrocarbons, —CH₂CH₂—, ═CR₂ and ═SiR₂ in a more particular    embodiment; wherein and R is selected from the group consisting of    alkyls, cycloalkyls, aryls, alkoxys, fluoroalkyls and    heteroatom-containing hydrocarbons in one embodiment; and R is    selected from the group consisting of C₁ to C₆ alkyls, substituted    phenyls, phenyl, and C₁ to C₆ alkoxys in a more particular    embodiment; and R is selected from the group consisting of methoxy,    methyl, phenoxy, and phenyl in yet a more particular embodiment;-   wherein A may be absent in yet another embodiment, in which case    each R* is defined as for R¹-R¹²;-   each X is as described above in (I);-   n is an integer from 0 to 4, and from 1 to 3 in another embodiment,    and 1 or 2 in yet another embodiment; and-   R¹ through R¹² are independently: selected from the group consisting    of hydrogen radical, halogen radicals, C₁ to C₁₋₂ alkyls, C₂ to C₁₂    alkenyls, C₆ to C₁₂ aryls, C₇ to C₂₀ alkylaryls, C₁ to C₁₂ alkoxys,    C₁ to C₁₂ fluoroalkyls, C₆ to C₁₂ fluoroaryls, and C₁ to C₁₂    heteroatom-containing hydrocarbons and substituted derivatives    thereof in one embodiment; selected from the group consisting of    hydrogen radical, fluorine radical, chlorine radical, bromine    radical, C₁ to C₆ alkyls, C₂ to C₆ alkenyls, C₇ to C₁₈ alkylaryls,    C₁ to C₆ fluoroalkyls, C₂ to C₆ fluoroalkenyls, C₇ to C₁₈    fluoroalkylaryls in a more particular embodiment; and hydrogen    radical, fluorine radical, chlorine radical, methyl, ethyl, propyl,    isopropyl, butyl, isobutyl, tertiary butyl, hexyl, phenyl,    2,6-di-methylpheyl, and 4-tertiarybutylpheyl groups in yet a more    particular embodiment; wherein adjacent R groups may form a ring,    either saturated, partially saturated, or completely saturated.

The structure of the metallocene catalyst component represented by (Va)may take on many forms such as disclosed in, for example, U.S. Pat. No.5,026,798, U.S. Pat. No. 5,703,187, and U.S. Pat. No. 5,747,406,including a dimer or oligomeric structure, such as disclosed in, forexample, U.S. Pat. No. 5,026,798 and U.S. Pat. No. 6,069,213.

In a particular embodiment of the metallocene represented in (Vd), R¹and R² form a conjugated 6-membered carbon ring system that may or maynot be substituted.

Non-limiting examples of metallocene catalyst components consistent withthe description herein include:

-   cyclopentadienylzirconium X_(n),-   indenylzirconium X_(n),-   (1-methylindenyl)zirconium X_(n),-   (2-methylindenyl)zirconium X_(n),-   (1-propylindenyl)zirconium X_(n),-   (2-propylindenyl)zirconium X_(n),-   (1-butylindenyl)zirconium X_(n),-   (2-butylindenyl)zirconium X_(n),-   (methylcyclopentadienyl)zirconium X_(n),-   tetrahydroindenylzirconium X_(n),-   (pentamethylcyclopentadienyl)zirconium X_(n),-   cyclopentadienylzirconium X_(n),-   pentamethylcyclopentadienyltitanium X_(n),-   tetramethylcyclopentyltitanium X_(n),-   1,2,4-trimethylcyclopentadienylzirconium X_(n),-   dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(cyclopentadienyl)zirconium    X_(n),-   dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(1,2,3-trimethyl-cyclopentadienyl)zirconium    X_(n),-   dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(1,2-dimethyl-cyclopentadienyl)zirconium    X_(n),-   dimethylsilyl(1,2,3,4-tetramethyl-cyclopentadienyl)(2-methylcyclopentadienyl)zirconium    X_(n),-   dimethylsilyl(cyclopentadienyl)(indenyl)zirconium X_(n),-   dimethylsilyl(2-methylindenyl)(fluorenyl)zirconium X_(n),-   diphenylsilyl(1,2,3,4-tetramethyl-cyclopentadienyl)(3-propylcyclopentadienyl)zirconium    X_(n),-   dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(3-t-butylcyclopentadienyl)zirconium    X_(n),-   dimethylgermyl(1,2-dimethylcyclopentadienyl)(3-isopropylcyclopentadienyl)zirconium    X_(n),-   dimethylsilyl(1,2,3,4-tetramethyl-cyclopentadienyl)(3-methylcyclopentadienyl)zirconium    X_(n),-   diphenylmethylidene(cyclopentadienyl)(9-fluorenyl)zirconium X_(n),-   diphenylmethylidene(cyclopentadienyl)(indenyl)zirconium X_(n),-   iso-propylidenebis(cyclopentadienyl)zirconium X_(n),-   iso-propylidene(cyclopentadienyl)(9-fluorenyl)zirconium X_(n),-   iso-propylidene(3-methylcyclopentadienyl)(9-fluorenyl)zirconium    X_(n),-   ethylenebis(9-fluorenyl)zirconium X_(n),-   meso-ethylenebis(1-indenyl)zirconium X_(n),-   ethylenebis(1-indenyl)zirconium X_(n),-   ethylenebis(2-methyl-1-indenyl)zirconium X_(n),-   ethylenebis(2-methyl-4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   ethylenebis(2-propyl-4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   ethylenebis(2-isopropyl-4,5,6,7-tetrahydro-1-indenyl)zirconium    X_(n),-   ethylenebis(2-butyl-4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   ethylenebis(2-isobutyl-4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   dimethylsilyl(4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   diphenyl(4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   dimethylsilylbis(cyclopentadienyl)zirconium X_(n),-   dimethylsilylbis(9-fluorenyl)zirconium X_(n),-   dimethylsilylbis(1-indenyl)zirconium X_(n),-   dimethylsilylbis(2-methylindenyl)zirconium X_(n),-   dimethylsilylbis(2-propylindenyl)zirconium X_(n),-   dimethylsilylbis(2-butylindenyl)zirconium X_(n),-   diphenylsilylbis(2-methylindenyl)zirconium X_(n),-   diphenylsilylbis(2-propylindenyl)zirconium X_(n),-   diphenylsilylbis(2-butylindenyl)zirconium X_(n),-   dimethylgermylbis(2-methylindenyl)zirconium X_(n),-   dimethylsilylbis(tetrahydroindenyl)zirconium X_(n),-   dimethylsilylbis(tetramethylcyclopentadienyl)zirconium X_(n),-   dimethylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium X_(n),-   diphenylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium X_(n),-   diphenylsilylbis(indenyl)zirconium X_(n),-   cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(cyclopentadienyl)zirconium    X_(n),-   cyclotetramethylenesilyl(tetramethylcyclopentadienyl)(cyclopentadienyl)zirconium    X_(n),-   cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(2-methylindenyl)zirconium    X_(n),-   cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(3-methylcyclopentadienyl)zirconium    X_(n),-   cyclotrimethylenesilylbis(2-methylindenyl)zirconium X_(n),-   cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(2,3,5-trimethylcyclopentadienyl)zirconium    X_(n),-   cyclotrimethylenesilylbis(tetramethylcyclopentadienyl)zirconium    X_(n),-   dimethylsilyl(tetramethylcyclopentadieneyl)(N-tert-butylamido)titanium    X_(n),-   bis(cyclopentadienyl)chromium X_(n),-   bis(cyclopentadienyl)zirconium X_(n),-   bis(n-butylcyclopentadienyl)zirconium X_(n),-   bis(n-dodecyclcyclopentadienyl)zirconium X_(n),-   bis(ethylcyclopentadienyl)zirconium X_(n),-   bis(iso-butylcyclopentadienyl)zirconium X_(n),-   bis(iso-propylcyclopentadienyl)zirconium X_(n),-   bis(methylcyclopentadienyl)zirconium X_(n),-   bis(n-oxtylcyclopentadienyl)zirconium X_(n),-   bis(n-pentylcyclopentadienyl)zirconium X_(n),-   bis(n-propylcyclopentadienyl)zirconium X_(n),-   bis(trimethylsilylcyclopentadienyl)zirconium X_(n),-   bis(1,3-bis(trimethylsilyl)cyclopentadienyl)zirconium X_(n),-   bis(1-ethyl-2-methylcyclopentadienyl)zirconium X_(n),-   bis(1-ethyl-3-methylcyclopentadienyl)zirconium X_(n),-   bis(pentamethylcyclopentadienyl)zirconium X_(n),-   bis(pentamethylcyclopentadienyl)zirconium X_(n),-   bis(1-propyl-3-methylcyclopentadienyl)zirconium X_(n),-   bis(1-n-butyl-3-methylcyclopentadienyl)zirconium X_(n),-   bis(1-isobutyl-3-methylcyclopentadienyl)zirconium X_(n),-   bis(1-propyl-3-butylcyclopentadienyl)zirconium X_(n),-   bis(1,3-n-butylcyclopentadienyl)zirconium X_(n),-   bis(4,7-dimethylindenyl)zirconium X_(n),-   bis(indenyl)zirconium X_(n),-   bis(2-methylindenyl)zirconium X_(n),-   cyclopentadienylindenylzirconium X_(n),-   bis(n-propylcyclopentadienyl)hafnium X_(n),-   bis(n-butylcyclopentadienyl)hafnium X_(n),-   bis(n-pentylcyclopentadienyl)hafnium X_(n),-   (n-propyl cyclopentadienyl)(n-butyl cyclopentadienyl)hafnium X_(n),-   bis[(2-trimethylsilylethyl)cyclopentadienyl]hafnium X_(n),-   bis(trimethylsilyl cyclopentadienyl)hafnium X_(n),-   bis(2-n-propylindenyl)hafnium X_(n),-   bis(2-n-butylindenyl)hafnium X_(n),-   dimethylsilylbis(n-propylcyclopentadienyl)hafnium X_(n),-   dimethylsilylbis(n-butylcyclopentadienyl)hafnium X_(n),-   bis(9-n-propylfluorenyl)hafnium X_(n),-   bis(9-n-butylfluorenyl)hafnium X_(n),-   (9-n-propylfluorenyl)(2-n-propylindenyl)hafnium X_(n),-   bis(1-n-propyl-2-methylcyclopentadienyl)hafnium X_(n),-   (n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)hafnium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cyclopropylamido)titanium    X_(n),-   dimethylsilyl(tetramethyleyclopentadienyl)(cyclobutylamido)titanium    X_(n),-   dimethylsilyl(tetramethyleyclopentadienyl)(cyclopentylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cycloheptylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cyclooctylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cyclononylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cyclodecylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cycloundecylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(sec-butylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(n-octylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(n-decylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(n-octadecylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclopropylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclobutylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclopentylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cycloheptylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclooctylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclononylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclodecylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cycloundecylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(sec-butylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(n-octylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(n-decylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(n-octadecylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclopropylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclobutylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclopentylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cycloheptylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclooctylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclononylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclodecylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cycloundecylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(sec-butylamido)titanium    X_(n),-   diphenylsilyl(tetramethyleyclopentadienyl)(n-octylamido)titanium    X_(n),-   diphenylsilyl(tetramethyleyclopentadienyl)(n-decylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(n-octadecylamido)titanium    X_(n), and derivatives thereof.

Wherein the value of n is 1, 2 or 3, and at least one X is a fluorideion. By “derivatives thereof”, it is meant any substitution or ringformation as described above for structures (Va-d) in one embodiment;and in particular, replacement of the metal “M” (Cr, Zr, Ti or Hf) withan atom selected from the group consisting of Cr, Zr, Hf and Ti; andreplacement of the “X” group with any of C₁ to C₅ alkyls, C₆ aryls, C₆to C₁₀ alkylaryls, fluorine, chlorine, or bromine. In a particularembodiment, each of the above metallocenes is a fluorided metallocenewherein one or more of the X groups is a fluoride; and all X groups arefluorides in yet a more particular embodiment.

More particularly, non-limiting examples of the fluorided catalystcomponents useful in the method of the invention are as follows:

-   Bis(methylcyclopentadienyl)zirconium difluoride,-   Bis(ethylcyclopentadienyl)zirconium difluoride,-   Bis(propylcyclopentadienyl)zirconium difluoride,-   Bis(isopropylcyclopentadienyl)zirconium difluoride,-   Bis(butylcyclopentadienyl)zirconium difluoride,-   Bis(isobutylcyclopentadienyl)zirconium difluoride,-   Bis(neopentylcyclopentadienyl)zirconium difluoride,-   Bis(cyclopentylcyclopentadienyl)zirconium difluoride,-   Bis(cyclohexylmethylcyclopentadienyl)zirconium difluoride,-   Bis(allylcyclopentadienyl)zirconium difluoride,-   Bis((3-butenyl)cyclopentadienyl)zirconium difluoride,-   Bis(trimethylsilylcyclopentadienyl)zirconium difluoride,-   Bis(trimethylgermylcyclopentadienyl)zirconium difluoride,-   Bis(trimethylsilylmethylcyclopentadienyl)zirconium difluoride,-   Bis(1,2-dimethylcyclopentadienyl)zirconium difluoride,-   Bis(1,3-dimethylcyclopentadienyl)zirconium difluoride,-   Bis(1,2,3-trimethylcyclopentadienyl)zirconium difluoride,-   Bis(1,2,4-trimethylcyclopentadienyl)zirconium difluoride,-   Bis(tetramethylcyclopentadienyl)zirconium difluoride,-   Bis(1,3-methylethylcyclopentadienyl)zirconium difluoride,-   Bis(1,3-methylpropylcyclopentadienyl)zirconium difluoride,-   Bis(1,3-methylbutylcyclopentadienyl)zirconium difluoride,-   Bis(phenylcyclopentadienyl)zirconium difluoride,-   Bis(1,3-methylphenylcyclopentadienyl)zirconium difluoride,-   Bis(benzylcyclopentadienyl)zirconium difluoride,-   Bis(1,3-methylbenzylcyclopentadienyl)zirconium difluoride,-   Bis(phenethylcyclopentadienyl)zirconium difluoride,-   Bis((3-phenylpropyl)cyclopentadienyl)zirconium difluoride,-   (Tetramethylcylopentadienyl)(propylcyclopentadienyl)zirconium    difluoride,-   (Pentamethylcylopentadienyl)(propylcyclopentadienyl)zirconium    difluoride,-   Cyclopentadienyl(propylcyclopentadienyl)zirconium difluoride,-   Cyclopentadienyl(butylcyclopentadienyl)zirconium difluoride,-   Cyclopentadienyl(cyclopentylcyclopentadienyl)zirconium difluoride,-   Cyclopentadienyl(tetrahydroindenyl)zirconium difluoride,-   Cyclopentadienyl(1,3-methylbutylcyclopentadienyl)zirconium    difluoride,-   Cyclopentadienyl(tetramethylcyclopentadienyl)zirconium difluoride,-   Cyclopentadienyl(propyltetramethylcyclopentadienyl)zirconium    difluoride,-   Cyclopentadienyl(butyltetramethylcyclopentadienyl)zirconium    difluoride,-   Cyclopentadienyl(cyclopentyltetramethylcyclopentadienyl)zirconium    difluoride,-   Cyclopentadienyl(indenyl)zirconium difluoride,-   Cyclopentadienyl(1-methylindenyl)zirconium difluoride,-   Cyclopentadienyl(fluorenyl)zirconium difluoride,-   Cyclopentadienyl(tetrahydrofluorenyl)zirconium difluoride,-   Cyclopentadienyl(octahydrofluorenyl)zirconium difluoride,-   Bis(tetrahydroindenyl)zirconium difluoride,-   Bis(trihydropentalenyl)zirconium difluoride,-   Bis(pentahydroazulenyl)zirconium difluoride,-   Dimethylsilylbis(tetrahydroindenyl)zirconium difluoride,-   Ethylenebis(tetrahydroindenyl)zirconium difluoride,-   Bis(indenyl)zirconium difluoride,-   Bis(1-methylindenyl)zirconium difluoride,-   Bis(2-methylindenyl)zirconium difluoride,-   Bis(4,7-dimethylindenyl)zirconium difluoride,-   Bis(5,6-dimethylindenyl)zirconium difluoride,-   Bis(1-phenylindenyl)zirconium difluoride,-   Bis(2-phenylindenyl)zirconium difluoride,-   Bis(fluorenyl)zirconium difluoride,-   Bis(1-methylfluorenyl)zirconium difluoride,-   Bis(2,7-di-t-butylfluorenyl)zirconium difluoride,-   Dimethylsilylbis(3-methylcyclopentadienyl)zirconium difluoride,-   Dimethylsilylbis(3-propylcyclopentadienyl)zirconium difluoride,-   Dimethylsilylbis(2,4-dimethylcyclopentadienyl)zirconium difluoride,-   Dimethylsilylbis(2,3,5-trimethylcyclopentadienyl)zirconium    difluoride,-   Dimethylsilylbis(tetramethylcyclopentadienyl)zirconium difluoride,-   Dimethylsilylbis(indenyl)zirconium difluoride,-   Dimethylsilylbis(2-methylindenyl)zirconium difluoride,-   Dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium difluoride,-   Dimethylsilylbis(2-methyl-4-(3,5-di-t-butyl)phenylindenyl)zirconium    difluoride,-   Dimethylsilylbis(2-methyl-4-naphthylindenyl)zirconium difluoride,-   Dimethylsilyl(cyclopentadienyl)(indenyl)zirconium difluoride,-   Dimethylsilyl(tetramethylcyclopentadienyl)(indenyl)zirconium    difluoride,-   Silacyclobutyl(tetramethylcyclopentadienyl)(indenyl)zirconium    difluoride,-   Silacyclopentyl(tetramethylcyclopentadienyl)(indenyl)zirconium    difluoride,-   Ethylenebis(indenyl)zirconium difluoride,-   Ethylenebis(2-methylindenyl)zirconium difluoride,-   Isopropylidene(cyclopentadienyl)(fluorenyl)zirconium difluoride,-   Diphenylmethylidene(cyclopentadienyl)(fluorenyl)zirconium    difluoride,-   Dimethylsilyl(cyclopentadienyl)(fluorenyl)zirconium difluoride,-   Diphenylsilyl(cyclopentadienyl)(fluorenyl)zirconium difluoride,-   Dimethylsilylbis(fluorenyl)zirconium difluoride,-   Ethylenebis(fluorenyl)zirconium difluoride,-   Bis(methylcyclopentadienyl)hafnium difluoride,-   Bis(ethylcyclopentadienyl)hafnium difluoride,-   Bis(propylcyclopentadienyl)hafnium difluoride,-   Bis(butylcyclopentadienyl)hafnium difluoride,-   Bis(isobutylcyclopentadienyl)hafnium difluoride,-   Bis(neopentylcyclopentadienyl)hafnium difluoride,-   Bis(cyclopentylcyclopentadienyl)hafnium difluoride,-   Bis(allylcyclopentadienyl)hafnium difluoride,-   Bis((3-butenyl)cyclopentadienyl)hafnium difluoride,-   Bis(cyclohexylmethylcyclopentadienyl)hafnium difluoride,-   Bis(trimethylsilylmethylcyclopentadienyl)hafnium difluoride,-   Bis((3-phenylpropyl)cyclopentadienyl)hafnium difluoride,-   Bis(1,3-methylbutylcyclopentadienyl)hafnium difluoride,-   Bis(1,3-methylpropylcyclopentadienyl)hafnium difluoride,-   Ethylenebis(indenyl)hafnium difluoride,-   Dimethylsilylbis(3-propylcyclopentadienyl)hafnium difluoride,-   Dimethylsilylbis(2,4-methylpropylcyclopentadienyl)hafnium    difluoride,-   Dimethylsilylbis(tetramethylcyclopentadienyl)hafnium difluoride,-   Dimethylsilylbis(indenyl)hafnium difluoride,-   Diphenylsilylbis(indenyl)hafnium difluoride,-   Bis(cyclopentadienyl)titanium difluoride,-   Bis(methylcyclopentadienyl)titanium difluoride,-   Bis(ethylcyclopentadienyl)titanium difluoride,-   Bis(propylcyclopentadienyl)titanium difluoride,-   Bis(butylcyclopentadienyl)titanium difluoride,-   Bis(isobutylcyclopentadienyl)titanium difluoride,-   Bis(neopentylcyclopentadienyl)titanium difluoride,-   Bis(cyclopentylcyclopentadienyl)titanium difluoride,-   Ethylenebis(indenyl)titanium difluoride,-   Dimethylsilylbis(indenyl)titanium difluoride,-   Diphenylsilyl(cyclopentadienyl)(fluorenyl)titanium difluoride,-   (cyclopentadienyl)zirconium trifluoride,-   (indenyl)zirconium trifluoride,-   (1-methylindenyl)zirconium trifluoride,-   (2-methylindenyl)zirconium trifluoride,-   (1-propylindenyl)zirconium trifluoride,-   (2-propylindenyl)zirconium trifluoride,-   (1-butylindenyl)zirconium trifluoride,-   (2-butylindenyl)zirconium trifluoride,-   (methylcyclopentadienyl)zirconium trifluoride,-   (tetrahydroindenyl)zirconium trifluoride,-   (pentamethylcyclopentadienyl)zirconium trifluoride,-   (cyclopentadienyl)zirconium trifluoride,-   pentamethylcyclopentadienyltitanium trifluoride,-   tetramethylcyclopentyldienyltitanium trifluoride,-   1,2,4-trimethylcyclopentadienylzirconium trifluoride, and mixtures    thereof.

It is contemplated that the metallocene catalysts components describedabove include their structural or optical or enantiomeric isomers(racemic mixture), and may be a pure enantiomer in one embodiment.

As used herein, a single, bridged, asymmetrically substitutedmetallocene catalyst component having a racemic and/or meso isomer doesnot, itself, constitute at least two different bridged, metallocenecatalyst components.

The “metallocene catalyst component” useful in the present invention maycomprise any combination of any “embodiment” described herein.

When combined to form the bimetallic catalyst component, the molar ratioof metal from the first catalyst component to the second catalystcomponent (e.g., molar ratio of Ti:Zr) is a value of from 0.1 to 20 inone embodiment; and from 1 to 18 in another embodiment, and from 2 to 15in yet another embodiment, and from 3 to 12 in yet another embodiment;and from 4 to 10 in yet another embodiment, and from 4 to 8 in yetanother embodiment; wherein a desirable molar ratio of first catalystcomponent metal:second catalyst component metal is any combination ofany upper limit with any lower limit described herein.

Activator

As used herein, the term “activator” is defined to be any compound orcombination of compounds, supported or unsupported, which can activate acatalyst compound (e.g., Ziegler-Natta, metallocenes, Group15-containing catalysts, etc.), such as by creating a cationic speciesfrom the catalyst component. Typically, this involves the abstraction ofat least one leaving group (X group in the formulas/structures above)from the metal center of the catalyst component. The catalyst componentsof the present invention are thus activated towards olefinpolymerization using such activators. Embodiments of such activatorsinclude Lewis acids such as cyclic or oligomericpoly(hydrocarbylaluminum oxides), alkylaluminum compounds and so callednon-coordinating ionic activators (“NCA”) (alternately, “ionizingactivators” or “stoichiometric activators”), or any other compound thatcan convert a neutral metallocene catalyst component to a metallocenecation that is active with respect to olefin polymerization.

More particularly, it is within the scope of this invention to use Lewisacids such as alumoxane (e.g., “MAO”), modified alumoxane (e.g.,“TIBAO”), and alkylaluminum compounds as activators, and/or ionizingactivators (neutral or ionic) such as tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)boron and/or a trisperfluorophenyl boronmetalloid precursors to activate desirable metallocenes describedherein. MAO and other aluminum-based activators are well known in theart. Ionizing activators are well known in the art and are described by,for example, Eugene You-Xian Chen & Tobin J. Marks, Cocatalysts forMetal-Catalyzed Olefin Polymerization: Activators, Activation Processes,and Structure-Activity Relationships 100(4) CHEMICAL REVIEWS 1391-1434(2000). The activators may be associated with or bound to a support,either in association with the catalyst component (e.g., metallocene) orseparate from the catalyst component, such as described by Gregory G.Hlatky, Heterogeneous Single-Site Catalysts for Olefin Polymerization100(4) CHEMICAL REVIEWS 1347-1374 (2000).

Non-limiting examples of aluminum alkyl compounds which may be utilizedas activators for the catalyst precursor compounds for use in themethods of the present invention include trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum and the like.

Examples of neutral ionizing activators include Group 13 tri-substitutedcompounds, in particular, tri-substituted boron, tellurium, aluminum,gallium and indium compounds, and mixtures thereof. The threesubstituent groups are each independently selected from the groupconsisting of alkyls, alkenyls, halogen, substituted alkyls, aryls,arylhalides, alkoxy and halides. In one embodiment, the three groups areindependently selected from the group consisting of halogen, mono ormulticyclic (including halosubstituted) aryls, alkyls, and alkenylcompounds and mixtures thereof. In another embodiment, the three groupsare selected from the group consisting of alkenyl groups having 1 to 20carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groupshaving 1 to 20 carbon atoms and aryl groups having 3 to 20 carbon atoms(including substituted aryls), and combinations thereof. In yet anotherembodiment, the three groups are selected from the group consisting ofalkyls having 1 to 4 carbon groups, phenyl, naphthyl and mixturesthereof. In yet another embodiment, the three groups are selected fromthe group consisting of highly halogenated alkyls having 1 to 4 carbongroups, highly halogenated phenyls, and highly halogenated naphthyls andmixtures thereof. By “highly halogenated”, it is meant that at least 50%of the hydrogens are replaced by a halogen group selected from the groupconsisting of fluorine, chlorine and bromine. In yet another embodiment,the neutral stoichiometric activator is a tri-substituted Group 13compound comprising highly fluorided aryl groups, the groups beinghighly fluorided phenyl and highly fluorided naphthyl groups.

In another embodiment, the neutral tri-substituted Group 13 compoundsare boron compounds such as a trisperfluorophenyl boron,trisperfluoronaphthyl boron, tris(3,5-di(trifluoromethyl)phenyl)boron,tris(di-t-butylmethylsilyl)perfluorophenylboron, and other highlyfluorinated trisarylboron compounds and combinations thereof, and theiraluminum equivalents. Other suitable neutral ionizing activators aredescribed in U.S. Pat. No. 6,399,532 B1, U.S. Pat. No. 6,268,445 B1, andin 19 ORGANOMETALLICS 3332-3337 (2000), and in 17 ORGANOMETALLICS3996-4003 (1998).

Illustrative, not limiting examples of ionic ionizing activators includetrialkyl-substituted ammonium salts such as triethylammoniumtetra(phenyl)boron, tripropylammonium tetra(phenyl)boron,tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammoniumtetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron,tributylammonium tetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-tri-fluoromethylphenyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boronand the like; N,N-dialkyl anilinium salts such as N,N-dimethylaniliniumtetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron,N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron and the like; dialkylammonium salts such as di-(isopropyl)ammoniumtetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boronand the like; and triaryl phosphonium salts such as triphenylphosphoniumtetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron,tri(dimethylphenyl)phosphonium tetra(phenyl)boron and the like, andtheir aluminum equivalents.

In yet another embodiment of the activator of the invention, analkylaluminum can be used in conjunction with a heterocyclic compound.The ring of the heterocyclic compound may includes at least onenitrogen, oxygen, and/or sulfur atom, and includes at least one nitrogenatom in one embodiment. The heterocyclic compound includes 4 or morering members in one embodiment, and 5 or more ring members in anotherembodiment.

The heterocyclic compound for use as an activator with an alkylaluminummay be unsubstituted or substituted with one or a combination ofsubstituent groups. Examples of suitable substituents include halogen,alkyl, alkenyl or alkynyl radicals, cycloalkyl radicals, aryl radicals,aryl substituted alkyl radicals, acyl radicals, aroyl radicals, alkoxyradicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals,alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals,alkyl- or dialkyl-carbamoyl radicals, acyloxy radicals, acylaminoradicals, aroylamino radicals, straight, branched or cyclic, alkyleneradicals, or any combination thereof. The substituents groups may alsobe substituted with halogens, particularly fluorine or bromine, orheteroatoms or the like.

Non-limiting examples of hydrocarbon substituents include methyl, ethyl,propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenylgroups and the like, including all their isomers, for example tertiarybutyl, isopropyl, and the like. Other examples of substituents includefluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl orchlorobenzyl.

In one embodiment, the heterocyclic compound is unsubstituted. Inanother embodiment one or more positions on the heterocyclic compoundare substituted with a halogen atom or a halogen atom containing group,for example a halogenated aryl group. In one embodiment the halogen isselected from the group consisting of chlorine, bromine and fluorine,and selected from the group consisting of fluorine and bromine inanother embodiment, and the halogen is fluorine in yet anotherembodiment.

Non-limiting examples of heterocyclic compounds utilized in theactivator of the invention include substituted and unsubstitutedpyrroles, imidazoles, pyrazoles, pyrrolines, pyrrolidines, purines,carbazoles, and indoles, phenyl indoles, 2,5,-dimethylpyrroles,3-pentafluorophenylpyrrole, 4,5,6,7-tetrafluoroindole or3,4-difluoropyrroles.

In one embodiment, the heterocyclic compound described above is combinedwith an alkyl aluminum or an alumoxane to yield an activator compoundwhich, upon reaction with a catalyst component, for example ametallocene, produces an active polymerization catalyst. Non-limitingexamples of alkylaluminums include trimethylaluminum, triethylaluminum,triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum,tri-iso-octylaluminum, triphenylaluminum, and combinations thereof.

Other activators include those described in WO 98/07515 such astris(2,2′, 2″-nonafluorobiphenyl)fluoroaluminate. Combinations ofactivators are also contemplated by the invention, for example,alumoxanes and ionizing activators in combinations. Other activatorsinclude aluminum/boron complexes, perchlorates, periodates and iodatesincluding their hydrates; lithium(2,2′-bisphenyl-ditrimethylsilicate).4THF; silylium salts in combinationwith a non-coordinating compatible anion. Also, methods of activationsuch as using radiation, electro-chemical oxidation, and the like arealso contemplated as activating methods for the purposes of renderingthe neutral metallocene-type catalyst compound or precursor to ametallocene-type cation capable of polymerizing olefins. Otheractivators or methods for activating a metallocene-type catalystcompound are described in for example, U.S. Pat. Nos. 5,849,852,5,859,653 and 5,869,723 and WO 98/32775.

In general, the activator and catalyst component(s) are combined in moleratios of activator to catalyst component from 1000:1 to 0.1:1 in oneembodiment, and from 300:1 to 1:1 in a more particular embodiment, andfrom 150:1 to 1:1 in yet a more particular embodiment, and from 50:1 to1:1 in yet a more particular embodiment, and from 10:1 to 0.5:1 in yet amore particular embodiment, and from 3:1 to 0.3:1 in yet a moreparticular embodiment, wherein a desirable range may include anycombination of any upper mole ratio limit with any lower mole ratiolimit described herein. When the activator is a cyclic or oligomericpoly(hydrocarbylaluminum oxide) (e.g., “MAO”), the mole ratio ofactivator to catalyst component ranges from 2:1 to 100,000:1 in oneembodiment, and from 10:1 to 10,000:1 in another embodiment, and from50:1 to 2,000:1 in a more particular embodiment. When the activator is aneutral or ionic ionizing activator such as a boron alkyl and the ionicsalt of a boron alkyl, the mole ratio of activator to catalyst componentranges from 0.5:1 to 10:1 in one embodiment, and from 1:1 to 5:1 in yeta more particular embodiment.

More particularly, the molar ratio of Al/metallocene-metal (Al from MAO)ranges from 40 to 500 in one embodiment; and ranges from 50 to 400 inanother embodiment; and ranges from 60 to 300 in yet another embodiment,and ranges from 70 to 200 in yet another embodiment; and ranges from 80to 175 in yet another embodiment; and ranges from 90 to 125 in yetanother embodiment, wherein a desirable molar ratio of Al(MAO) tometallocene-metal “M” can be any combination of any upper limit with anylower limit described herein.

Supports

A support may also be present as part of the bimetallic catalyst systemof the invention. Supports, methods of supporting, modifying, andactivating supports for single-site catalyst such as metallocenes isdiscussed in, for example, 1 METALLOCENE-BASED POLYOLEFINS 173-218 (J.Scheirs & W. Kaminsky eds., John Wiley & Sons, Ltd. 2000). The terms“support” or “carrier”, as used herein, are used interchangeably andrefer to any support material, a porous support material in oneembodiment, including inorganic or organic support materials.Non-limiting examples of support materials include inorganic oxides andinorganic chlorides, and in particular such materials as talc, clay,silica, alumina, magnesia, zirconia, iron oxides, boria, calcium oxide,zinc oxide, barium oxide, thoria, aluminum phosphate gel, glass beads,and polymers such as polyvinylchloride and substituted polystyrene,functionalized or crosslinked organic supports such as polystyrenedivinyl benzene polyolefins or polymeric compounds, and mixturesthereof, and graphite, in any of its various forms.

The support may be contacted with the other components of the catalystsystem in any number of ways. In one embodiment, the support iscontacted with the activator to form an association between theactivator and support, or a “bound activator”. In another embodiment,the catalyst component may be contacted with the support to form a“bound catalyst component”. In yet another embodiment, the support maybe contacted with the activator and catalyst component together, or witheach partially in any order. The components may be contacted by anysuitable means as in a solution, slurry, or solid form, or somecombination thereof, and may be heated to any desirable temperature toeffectuate a desirable chemical/physical transformation.

Desirable carriers are inorganic oxides that include Group 2, 3, 4, 5,13 and 14 oxides and chlorides in one embodiment, and more particularly,inorganic oxides and chlorides of Group 13 and 14 atoms. Yet moreparticularly, support materials include silica, alumina, silica-alumina,magnesium chloride, graphite, and mixtures thereof. Other usefulsupports include magnesia, titania, zirconia, montmorillonite (EP 0 511665 B1), phyllosilicate, and the like. Also, combinations of thesesupport materials may be used, for example, silica-chromium,silica-alumina, silica-titania and the like. Additional supportmaterials may include those porous acrylic polymers described in EP 0767 184 B1.

In one aspect of the support useful in the invention, the supportpossess a surface area in the range of from 10 to 700 m²/g, pore volumein the range of from 0.1 to 4.0 cm³/g and average particle size in therange of from 5 to 500 μm. In another embodiment, the surface area ofthe carrier is in the range of from 50 to 500 m²/g, pore volume of from0.5 to 3.5 cm³/g and average particle size of from 10 to 200 μm. In yetanother embodiment, the surface area of the carrier is in the range isfrom 100 to 400 m²/g, pore volume from 0.8 to 3.0 cm³/g and averageparticle size is from 5 to 100 μm. The average pore size of the carrierof the invention typically has pore size in the range of from 10 to 1000Å, from 50 to 500 Å in another embodiment, and from 75 to 350 Å in yetanother embodiment.

In one embodiment of the support, graphite is used as the support. Thegraphite is a powder in one embodiment. In another embodiment, thegraphite is flake graphite. In another embodiment, the graphite and hasa particle size of from 1 to 500 microns, from 1 to 400 microns inanother embodiment, and from 1 to 200 in yet another embodiment, andfrom 1 to 100 microns in yet another embodiment.

Dehydration or calcining of the support may or may also be carried out.In one embodiment, the support is calcined prior to reaction with thefluorine or other support-modifying compound. In another embodiment, thesupport is calcined and used without further modification, or calcined,followed by contacting with one or more activators and/or catalystcomponents. Suitable calcining temperatures range from 100° C. to 1500°C. in one embodiment, and from 200° C. to 1200° C. in anotherembodiment, and from 300° C. to 1000° C. in another embodiment, and from350° C. to 900° C. in yet another embodiment, and from 400° C. to 850°C. in yet a more particular embodiment, and from 800° C. to 900° C. inyet a more particular embodiment, and from 810° C. to 890° C. in yet amore particular embodiment, wherein a desirable range comprises anycombination of any upper temperature limit with any lower temperaturelimit. Calcining may take place in the absence of oxygen and moisture byusing, for example, an atmosphere of dry nitrogen.

The support, especially an inorganic support or graphite support, may bepretreated such as by a halogenation process or other suitable processthat, for example, associates a chemical species with the support eitherthrough chemical bonding, ionic interactions, or other physical orchemical interaction. In one embodiment, the support is fluorided. Thefluorine compounds suitable for providing fluorine for the support aredesirably inorganic fluorine containing compounds. Such inorganicfluorine containing compounds may be any compound containing a fluorineatom as long as it does not contain a carbon atom. Particularlydesirable are inorganic fluorine containing compounds selected from thegroup consisting of NH₄BF₄, (NH₄)₂SiF₆, NH₄PF₆, NH₄F, (NH₄)₂TaF₇,NH₄NbF₄, (NH₄)₂GeF₆, (NH₄)₂SmF₆, (NH₄)₂TiF₆, (NH₄)₂ZrF₆, MoF₆, ReF₆,GaF₃, SO₂ClF, F₂, SiF₄, SF₆, ClF₃, ClF₅, BrF₅, IF₇, NF₃, HF, BF₃, NHF₂and NH₄HF₂.

A desirable method of treating the support with the fluorine compound isto dry mix the two components by blending at a concentration of from0.01 to 10.0 millimole F/g of support in one embodiment, and in therange of from 0.05 to 6.0 millimole F/g of support in anotherembodiment, and in the range of from 0.1 to 3.0 millimole F/g of supportin yet another embodiment. The fluorine compound can be dry mixed withthe support either before or after charging to the vessel fordehydration or calcining the support. Accordingly, the fluorineconcentration present on the support is in the range of from 0.2 to 5 wt% in one embodiment, and from 0.6 to 3.5 wt % of support in anotherembodiment.

Another method of treating the support with the fluorine compound is todissolve the fluorine in a solvent, such as water, and then contact thesupport with the fluorine containing solution. When water is used andsilica is the support, it is desirable to use a quantity of water thatis less than the total pore volume of the support. Desirably, thesupport and, for example, fluorine compounds are contacted by anysuitable means such as by dry mixing or slurry mixing at a temperatureof from 100° C. to 1000° C. in one embodiment, and from 200° C. to 800°C. in another embodiment, and from 300° C. to 600° C. in yet anotherembodiment, the contacting in any case taking place for between two toeight hours.

It is within the scope of the present invention to co-contact (or“co-immobilize”) more than one catalyst component with a support.Non-limiting examples of co-immobilization of catalyst componentsinclude two or more of the same or different metallocene catalystcomponents, one or more metallocene with a Ziegler-Natta type catalyst,one or more metallocene with a chromium or “Phillips” type catalyst, oneor more metallocenes with a Group 15 containing catalyst, and any ofthese combinations with one or more activators. More particularly,co-supported combinations include metallocene A/metallocene A;metallocene A/metallocene B; metallocene/Ziegler Natta;metallocene/Group 15 containing catalyst; metallocene/chromium catalyst;metallocene/Ziegler Natta/Group 15-containing catalyst;metallocene/chromium catalyst/Group 15 containing catalyst, any of thethese with an activator, and combinations thereof.

Further, the catalyst system of the present invention can include anycombination of activators and catalyst components, either supported ornot supported, in any number of ways. For example, the catalystcomponent may include any one or both of metallocenes and/or Group15-containing catalysts components (e.g., U.S. Pat. No. 6,265,505; U.S.Pat. No. 5,707,913; EP 0 893 454; and WO 99/01460), and may include anycombination of activators, any of which may be supported by any numberof supports as described herein. Non-limiting examples of catalystsystem combinations useful in the present invention include MN+NCA;MN:S+NCA; NCA:S+MN; MN:NCA:S; MN+AlA; MN:S+AlA; AlA:S+MN; MN:AlA:S;AlA:S+NCA+MN; NCA:S+MN+AlA; G15+NCA; G15:S+NCA; NCA:S+G15; G15:NCA:S;G15+AlA; G15:S+AlA; AlA:S+G15; G15:AlA:S; AlA:S+NCA+G15; NCA:S+G15+AlA;MN+NCA+G15; MN:S+NCA+G15; NCA:S+MN+G15; MN:NCA:S+G15; MN+G15+AlA;MN:S+AlA+G15; AlA:S+MN+G15; MN:AlA:S+G15; AlA:S+NCA+MN+G15;NCA:S+MN+AlA+G15; MN+NCA; G15:MN:S+NCA; G15:NCA:S+MN; G15:MN:NCA:S;G15:MN:S+AlA; G15:AlA:S+MN; G15:MN:AlA:S; G15:AlA:S+NCA+MN;G15:NCA:S+MN+AlA; MN+ZN+NCA; MN:S+ZN+NCA; NCA:S+ZN+MN; ZN:MN:NCA:S;MN+ZN+AlA; MN:ZN:S+AlA; AlA:S+ZN+MN; MN:AlA:ZN:S; AlA:ZN:S+NCA+MN;MN:AlA:S+ZN; wherein “MN” is metallocene component, “ZN” is aZiegler-Natta catalyst component, such as described above for the firstcatalyst component, “NCA” is a non-coordinating activator includingionic and neutral boron and aluminum based compounds as described above,“AlA” is an aluminum alkyl and/or alumoxane based activator, “G15” is aGroup 15-containing catalyst component as described above, and “S” is asupport; and wherein the use of “:” with “S” means that that thosegroups next to the colon are associated with (“supported by”) thesupport as by pretreatment and other techniques known in the art, andthe “+” sign means that the additional component is not directly boundto the support but present with the support and species bound to thesupport, such as present in a slurry, solution, gas phase, or anotherway, but is not meant to be limited to species that have nophysico-chemical interaction with the support and/or supported species.Thus, for example, the embodiment “MN:NCA:S+G15” means that ametallocene and NCA activator are bound to a support, and present in,for example, a gas phase polymerization with a Group 15 containingcatalyst component.

In a particular embodiment, the catalyst system is selected from thegroup consisting of MN:ZN:NCA:S; MN:ZN:AlA:S; MN:AlA:S+ZN; ZN:AlA:S+MN;MN:NCA:S+ZN; and ZN:MN:AlA:NCA:S. The components may be combined in anyorder desirable to achieve the highest polymerization activity. In oneembodiment, the ZN catalyst is immobilized prior to immobilizing themetallocene; in another embodiment, the metallocene is firstimmobilized, and in yet another embodiment, an activator is firstimmobilized, followed by either the metallocene and/or the ZN catalyst.In yet another embodiment, both the MN and ZN catalyst components areimmobilized simultaneously on the support, the support being pretreatedwith activator in one embodiment, and treated after catalyst componenttreatment in yet another embodiment.

One embodiment of the support useful in the present invention is a socalled “enhanced support”, prepared by heating support particles at adehydration temperature of at least 800° C. or more, and between 800° C.and 1000° C. in another embodiment, resulting in an enhanced supporthaving a modified chemical structure. In a particular embodiment, theheating of the support takes place in an inert (e.g., N₂ or Ar)atmosphere, and in the absence of water. In preferred embodiments,increased productivity is achieved when the enhanced support is combinedwith the other parts of the bimetallic catalyst discussed herein, toform a supported bimetallic catalyst, which is then contacted withmonomers during polymerization to produce a bimodal polyolefincompositions.

In one or more specific embodiments, an enhanced support is firstprepared, preferably in the manner described below; then that enhancedsupport is treated (e.g., combined with ingredients that form the firstcatalyst) to provide a supported catalyst that includes the firstcatalyst component. In specific embodiments, that supported firstcatalyst is then treated in the presence of the second catalystcomponent to provide a supported bimetallic catalyst.

The enhanced support is prepared by any suitable means, and moreparticularly, by any means wherein water is removed from the support,such as by heating, exposure to low pressure, chemical treatment, orcombinations thereof. Heating the support at a dehydration temperatureof at least 800° C., and between 800° C. and 1000° C. in a particularembodiment, provides an enhanced support, for example, enhanced silica,which provides surprisingly improved results over support that isdehydrated at lower temperatures, that is, below 800° C., even slightlylower temperatures, for example, 760° C. While not immediately apparentfrom the enhancement procedure itself, it is contemplated that the heattreatment results in an actual chemical and/or physical change in thesupport structure itself, which only reveals its beneficial structurewhen combined with a first and second catalyst components describedherein, and placed in the context of an actual polymerization. Forexample, when the enhanced silica is combined with both the firstcatalyst component and the second catalyst component to form a supportedbimetallic catalyst composition, that supported bimetallic catalystcomposition, including the enhanced silica, has been discovered ashaving desirably high productivity when used in a polymerization processfor making bimodal polyolefin in a single reactor. For example, aproductivity of at least 3000 grams polymer/gram catalyst can beachieved. More preferably, the bimetallic catalyst that includes theenhanced support has a productivity of at least 3500 grams polymer/gramcatalyst. Even more preferably yet, a bimetallic catalyst having theenhanced support has a productivity of at least 4000 grams polymer/gramcatalyst. Other specific embodiments of the invention include bimetalliccatalysts with productivities of 4500 grams polymer/gram catalyst andabove, 5000 grams polymer/gram catalyst and above, or even 6000 gramspolymer/gram catalyst and above.

In a particular embodiment, the support useful in the present inventionis a Group 13 or 14 inorganic oxide support having a pore volume rangingfrom 0.8 to 3 cm³/g and a surface area of from 100 to 500 m²/g. Thissupport is desirably dehydrated as described herein in one embodiment. Apreferred support is an amorphous high surface area silica, such asDavison 952 or Sylopol® 955, sold by Davison Chemical Division of W.R.Grace and Company. Those silicas are in spherical form, prepared by thespray drying process, with a surface area of 300 m²/g and a pore volumeof 1.65 cm³/g. A procedure for dehydrating the silica at 600° C. is setforth in U.S. Pat. No. 5,525,678.

The enhanced support is then combined with a non-polar hydrocarbondiluent to form a support slurry, which can be stirred and optionallyheated during mixing.

A variety of non-polar hydrocarbon diluents can be used to form thesupport slurry, but any non-polar hydrocarbon selected should remain inliquid form at all relevant reaction temperatures, and the ingredientsused to form the first catalyst component should be at least partiallysoluble in the non-polar hydrocarbon. Accordingly, the non-polarhydrocarbon diluent is considered to be a “solvent” herein, even thoughin certain embodiments the ingredients are only partially soluble in thehydrocarbon.

Examples of suitable non-polar hydrocarbons include C₄-C₁₀ linear orbranched alkanes, cycloalkanes and aromatics. More specifically, anon-polar alkane can be isopentane, hexane, isohexane, n-heptane,octane, nonane, or decane; a non-polar cycloalkane such as cyclohexane;or an aromatic such as benzene, toluene, or ethylbenzene. Mixtures ofdifferent non-polar hydrocarbons can also be used.

The support slurry can be heated both during and after mixing of thesupport particles with the non-polar hydrocarbon solvent, but at thepoint when either or both of the catalysts are combined with the supportslurry, the temperature of the slurry should be sufficiently low so thatneither of the catalysts are inadvertently deactivated. Thus, thetemperature of the support slurry (e.g., silica slurry) is preferablymaintained at a temperature below 90° C., for example, from 25 to 70°C., or from 40 to 60° C. in another embodiment.

Gas Phase Polymerization Process

The bimetallic catalysts, and more particularly, the supportedbimetallic catalyst composition, described herein are preferably used tomake bimodal polyolefin compositions, that is, compositions having abimodal molecular weight distribution; in a particular embodiment, thebimetallic catalysts described herein are used in a singlepolymerization reactor to make the bimodal polyolefin composition. Oncethe supported bimetallic catalyst composition is prepared, as describedabove, a variety of processes can be carried out using that composition.Among the varying approaches that can be used include procedures setforth in U.S. Pat. No. 5,525,678 in which those processes are modifiedin accordance with the inventions claimed herein, for example, involvingthe high fluidized bulk density as described herein. The equipment,process conditions, reactants, additives and other materials will ofcourse vary in a given process, depending on the desired composition andproperties of the polymer being formed. For example, the processesdiscussed in any of the following patents can be used: U.S. Pat. Nos.6,420,580; 6,388,115; 6,380,328; 6,359,072; 6,346,586; 6,340,730;6,339,134; 6,300,436; 6,274,684; 6,271,323; 6,248,845; 6,245,868;6,245,705; 6,242,545; 6,211,105; 6,207,606; 6,180,735; and 6,147,173.

More particularly, the process of the present invention is directedtoward a gas phase polymerization process of one or more olefin monomershaving from 2 to 30 carbon atoms, from 2 to 12 carbon atoms in a moreparticular embodiment, and from 2 to 8 carbon atoms in yet a moreparticular embodiment. The invention is particularly well suited to thepolymerization of two or more olefin monomers of ethylene, propylene,1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,4-methyl-1-pentene, 1-isobutene, 1-isobutene and 1-decene.

Other monomers useful in the process of the invention includeethylenically unsaturated monomers, diolefins having 4 to 18 carbonatoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers andcyclic olefins. Non-limiting monomers useful in the invention mayinclude norbornene, norbornadiene, isobutylene, isoprene,vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidenenorbornene, dicyclopentadiene and cyclopentene.

In the most preferred embodiment of the process of the invention, acopolymer of ethylene is produced, where with ethylene, a comonomerhaving at least one α-olefin having from 4 to 15 carbon atoms, from 4 to12 carbon atoms in yet a more particular embodiment, and from 4 to 8carbon atoms in yet a more particular embodiment, is polymerized in agas phase process.

In another embodiment of the process of the invention, ethylene orpropylene is polymerized with at least two different comonomers,optionally one of which may be a diene, to form a terpolymer.

Typically in a gas phase polymerization process a continuous cycle isemployed where in one part of the cycle of a reactor system, a cyclinggas stream, otherwise known as a recycle stream or fluidizing medium, isheated in the reactor by the heat of polymerization. This heat isremoved from the recycle composition in another part of the cycle by acooling system external to the reactor. Generally, in a gas fluidizedbed process for producing polymers, a gaseous stream containing one ormore monomers is continuously cycled through a fluidized bed in thepresence of a catalyst under reactive conditions. The gaseous stream iswithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product is withdrawn from the reactor and freshmonomer is added to replace the polymerized monomer. (See for exampleU.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749,5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228.)

The reactor pressure in a gas phase process may vary from 100 psig (690kPa) to 500 psig (3448 kPa) in one embodiment, from 200 psig (1379 kPa)to 400 psig (2759 kPa) in a more particular embodiment, and from 250psig (1724 kPa) to 350 psig (2414 kPa) in yet a more particularembodiment.

The reactor temperature in a gas phase process may vary from 30° C. to120° C. in one embodiment, from 60° C. to 115° C. in a more particularembodiment, from 70° C. to 110° C. in yet a more particular embodiment,and from 70° C. to 95° C. in yet a more particular embodiment, or as setout further below.

In an embodiment of the invention, the process is operated byintroducing a carboxylate metal salt such as aluminum stearate or othermetal-fatty acid compound into the reactor and/or contacting acarboxylate metal salt with the catalyst system of the invention priorto its introduction into the reactor.

The “catalyst system” useful in the gas phase polymerization process ofthe invention includes the first and second catalyst components, makingup a bimetallic catalyst, and one or more activators. The bimetalliccatalyst is activated by any suitable means known in the art, eitherbefore introduction into the polymerization reactor or in situ. Thesupported bimetallic catalyst is fed to the reactor in a dry (nodiluent) state in a particular embodiment. In another embodiment, thebimetallic catalyst is suspended in a diluent (e.g., C₅ to C₁₅hydrocarbon) comprising from 5 wt % to 100 wt % mineral oil or siliconoil and fed into the reactor.

The gas-phase process of the present invention includes contacting thecatalyst system (including catalyst components and activators, andoptionally, a support) with monomers in a reactor vessel of desirableconfiguration to form a polyolefin. In one embodiment, the contactingmay take place in a first reactor vessel, followed by transfer of theformed polymer into another second, third etc. reactor vessel to allowfurther polymerization, optionally by adding the same or differentmonomers and optionally by adding the same or different catalystcomponents, activators, etc. In a particular embodiment of the presentinvention, the bimetallic catalyst system is contacted with monomers ina single reactor vessel (or “reactor”), followed by isolation of afinished polyolefin resin.

For example, a gas phase polymerization process claimed herein mayinclude use of a continuous cycle in which a cycling gas stream (i.e., arecycle stream or fluidizing medium) is heated in the reactor by theheat of polymerization. This heat can be removed from the recycle streamin another part of the cycle by a cooling system that is external to thereactor. In a gas fluidized bed process for producing polymers, agaseous stream containing one or more monomers can be continuouslycycled through a fluidized bed in the presence of a catalyst underreactive conditions. The gaseous stream is preferably withdrawn from thefluidized bed and then recycled back into the reactor. Polymer productcan be withdrawn from the reactor and fresh monomer added to replace thepolymerized monomer. (See for example U.S. Pat. Nos. 4,543,399,4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304,5,453,471, 5,462,999, 5,616,661 and 5,668,228)

The reactor pressure in a gas phase process may vary from 100 psig (690kPa) to 500 psig (3448 kPa) in one embodiment, from 200 psig (1379 kPa)to 400 psig (2759 kPa) in a particular embodiment, and from 250 psig(1724 kPa) to 350 psig (2414 kPa) in yet a more particular embodiment.

In one aspect of the invention, the voidage of the gas phase reactor isdesirably controlled. In one embodiment, the polymerization process ofthe invention is characterized as a process of polymerization using abimetallic catalyst wherein the voidage of the fluidized bed gas phasereactor is maintained at less than 40%. This can be accomplished by anysuitable means such as by, for example, adjusting the hydrogen level inthe reactor or reactors. The voidage of the reactor can be described inthe equation below (A): $\begin{matrix}{{Voidage} = \frac{{SBD} - {FBD}}{{SBD} - {{gas}\quad{density}}}} & (A)\end{matrix}$wherein SBD is the “settled bulk density” of the formed resin granulesin the reactor; FBD is the “fluidized bulk density”, which is thedensity of the resin granules in the reactor; and “gas density” issimply the density of the gas in the reactor. The FBD is the ratio ofthe measured pressure drop upward across a centrally fixed portion ofthe reactor to the height of the fixed portion. As noted therein, theFBD is a mean value, which may be greater or less than the localizedbulk density at any point in the fixed reactor portion. Since the gasdensity is diminishingly small, the equation describing voidage can besimplified to the following (B): $\begin{matrix}{{Voidage} = {1 - \frac{FBD}{SBD}}} & (B)\end{matrix}$

Certain specific embodiments of the invention are advantageouslydirected to a process having fluidized bulk density (FBD) that is higherthan other bimodal polyolefin polymerization processes. A high FBD (orlow voidage) can have benefits in a gas phase polymerization process,since higher FBD generally means higher catalyst productivity due to thehigher residence times allowable in such a reactor. A high FBD alsoprovides for advantages for restarting a commercial-scale reactor when agas phase polymerization cycle is interrupted by extraneous factors. Forexample, a low FBD corresponds to excessive bed expansion during therestarting process, and can sometimes even make the restart processunsuccessful.

As used herein, the term “fluidized bulk density” (FBD) has the samemeaning given that same term in U.S. Pat. No. 5,436,304, in which theterm is defined as the ratio of the measured pressure drop upward acrossa centrally fixed portion of the reactor to the height of the fixedportion, for example, a “pressure tap vertical separation.” As notedtherein, the FBD is a mean value, which may be greater or less than thelocalized bulk density at any point in the fixed reactor portion.

All FBD values that are absolute values of fluidized bulk density areexpressed in units of lbs/ft³. The values of FBD of the presentinvention range from 5 to 50 lbs/ft³ in one embodiment, from 7 to 40lbs/ft³ in a more particular embodiment, and from 8 to 30 lbs/ft³ in yeta more particular embodiment, and from 10 to 25 lbs/ft³ in yet anotherembodiment, wherein a desirable range for FBD may be any combination ofany upper limit with any lower limit.

All SBD values are expressed in units of lbs/ft³. The values of SBD ofthe present invention range from 10 to 60 lbs/ft³ in one embodiment, andfrom 12 to 50 lbs/ft³ in a more particular embodiment, and from 14 to 40lbs/ft³ in yet another embodiment, and from 15 to 35 lbs/ft³ in yetanother embodiment, wherein a desirable range for SBD may be anycombination of any upper limit with any lower limit.

In one embodiment, the voidage of the reactor is less than 50%(expressing the values above as percentages), and less than 45% in amore particular embodiment, and less than 40% in yet a more particularembodiment, and less than 35% in a particular embodiment, and less than30% in a more particular embodiment, and less than 20% in a moreparticular embodiment; and at least 5% in one embodiment, and at least10% in a more particular embodiment, wherein a desirable range ofvoidage values may include any combination of any upper voidage limitwith any lower voidage limit described herein. Stated another way, theFBD/SBD ratio may have a value of from greater than 0.40 (or 40% whenmultiplied by 100 as in the data tables) in one embodiment, and greaterthan 45% in a more particular embodiment, and greater than 50% in yet amore particular embodiment, and greater than 60% in yet a moreparticular embodiment, and greater than 65% in yet a more particularembodiment; and less than 95% in one embodiment, and less than 90% inyet another embodiment, and less than 85% in yet a more particularembodiment, wherein a desirable range of FBD/SBD values may include anycombination of any upper FBD/SBD limit with any lower FBD/SBD limitdescribed herein.

It has been found that the voidage can be adjusted to a desirable levelwhen using bimetallic catalyst systems comprising at least onemetallocene by adjusting the level of hydrogen in the polymerizationreactor. The level of hydrogen in the reactor can be adjusted byadjusting the level of hydrogen in the gas stream that is introducedinto the reactor, or stated alternately, adjusting the ratio of hydrogenand ethylene.

In certain specific embodiments, the polymerization reactor temperatureis maintained at a certain level to further optimize the voidage at adesirable level. As used herein, the term “reactor temperature” canrefer to an actual measured temperature (i.e., at a point in time) of afluidized bed in a reaction zone of a fluidized bed reactor used tocarry out a gas phase polymerization; and can also refer to a calculatednumber that equals an average of a plurality of actual measuredtemperatures, measured intermittently over a period of time, forexample, an average of ten measured temperatures over a four-hourperiod. In a particular embodiment, the polymerization reactortemperature ranges from 100° C., or 99° C., or 98° C., or 97° C., or 96°C., or 95° C., or 94° C., or 93° C., or 92° C., or 91° C., or 90° C., to40° C., 50° C., 60° C., 70° C., or 80° C., or 82° C., or 84° C., or 86°C., or 88° C., or 90° C., wherein the reactor temperature may be in arange from any combination of any upper temperature limit with any lowertemperature limit described herein. Thus, for example, a reactortemperature that averages 97° C. for at least a one, two, three, four ormore-hour period may be utilized during a continuous gas phasepolymerization cycle of the invention in one embodiment.

The voidage (or FBD) may be controlled in one embodiment by adjustingthe hydrogen level in the polymerization process. The hydrogen levels(also referred to as hydrogen amounts) are sometimes expressed herein interms of the molar ratio of H₂ to C₂ (also H₂/C₂ or H₂:C₂), wherein H₂refers to molecular hydrogen, and C₂ refers to ethylene. Alternatively,the hydrogen levels discussed herein can refer to the ratio of moles H₂to moles of monomers used in the polymerization reaction, for example,ethylene, propylene and/or butene. Preferably, however, the hydrogenlevel referenced herein is the molar ratio of hydrogen gas to ethylenemonomers. As with reactor temperature, the hydrogen levels referencedherein and in the claims include actual instantaneous measured hydrogenlevels, for example, a molar ratio of hydrogen gas to ethylene, or anaverage hydrogen level, based on measured hydrogen levels takenintermittently over a period of time.

The ratio of hydrogen to ethylene has an upper limit of 0.015 in oneembodiment, and an upper limit of 0.01 in another embodiment, 0.009 inyet another embodiment, and 0.008 in a more particular embodiment, and0.007 in yet a more particular embodiment, and 0.006 in yet a moreparticular embodiment, and 0.005 in yet a more particular embodiment,and 0.004 in yet a more particular embodiment. Thus, for example, theaverage ratio of a molecular hydrogen to ethylene over a four-hourperiod is 0.009 or below during a continuous gas phase polymerizationcycle in one embodiment. The ratio of hydrogen to ethylene may have alower limit of 0.0005 in another embodiment, and 0.001 in a moreparticular embodiment, and 0.002 in yet a more particular embodiment,and 0.003 in yet a more particular embodiment, and 0.004 in yet a moreparticular embodiment, and 0.005 in yet a more particular embodiment.The range of hydrogen levels (molar ratios of H₂/C₂) may have compriseany combination of any upper ratio limit with any lower ratio limitdescribed herein. For example, in a specific embodiment, the molar ratioof the hydrogen gas in the gaseous stream to ethylene in the gaseousstream is from 0.003 to 0.009.

An alkylaluminum compound, or mixture of compounds, such astrimethylaluminum or triethylaluminum is feed into the reactor in oneembodiment at a rate of from 10 wt. ppm to 500 wt. ppm (weight parts permillion alkylaluminum feedrate compared to ethylene feed rate), and from50 wt. ppm to 400 wt. ppm in a more particular embodiment, and from 60wt. ppm to 300 wt. ppm in yet a more particular embodiment, and from 80wt. ppm to 250 wt. ppm in yet a more particular embodiment, and from 75wt. ppm to 150 wt. ppm in yet another embodiment, wherein a desirablerange may comprise any combination of any upper limit with any lowerlimit. The alkylaluminum can be represented by the general formula AlR₃,wherein each R is the same or different and independently selected fromC₁ to C₁₀ alkyls and alkoxys.

Also, water may also be fed into the reactor in another embodiment at arate of from 0.01 wt. ppm to 200 wt. ppm (weight parts per million waterfeedrate compared to ethylene feed rate), and from 0.1 wt. ppm to 150wt. ppm in another embodiment, and from 0.5 wt. ppm to 100 wt. ppm inyet another embodiment, and from 1 wt. ppm to 60 wt. ppm in yet anotherembodiment, and from 5 wt. ppm to 40 wt. ppm in yet a more particularembodiment, wherein a desirable range may comprise any combination ofany upper limit with any lower limit described herein.

Bimodal Polymer Product and Films Made Therefrom

The polymers produced by the processes described herein, utilizing thebimetallic catalysts described herein, which are preferably bimodal, canbe used in a wide variety of products and end-use applications such asfilms, pipes and tubing, wire coating, and other applications. Thepolymers produced by the process of the invention include linear lowdensity polyethylene, elastomers, plastomers, high densitypolyethylenes, medium density polyethylenes, low density polyethylenes,polypropylene and polypropylene copolymers.

Polymers that can be made using the described processes can have avariety of compositions, characteristics and properties. At least one ofthe advantages of the bimetallic catalysts is that the process utilizedcan be tailored to form a polymer composition with a desired set ofproperties. For example, it is contemplated that the polymers having thesame properties as the bimodal polymer compositions in U.S. Pat. No.5,525,678 can be formed. Accordingly, U.S. Pat. No. 5,525,678. Also, thebimetallic catalysts described herein can be used in polymerizationprocesses to form polymers having the same properties as the polymers inthe following patents: U.S. Pat. Nos. 6,420,580; 6,388,115; 6,380,328;6,359,072; 6,346,586; 6,340,730; 6,339,134; 6,300,436; 6,274,684;6,271,323; 6,248,845; 6,245,868; 6,245,705; 6,242,545; 6,211,105;6,207,606; 6,180,735; and 6,147,173.

The polymers, typically ethylene based polymers, have a density in therange of from 0.860 g/cm³ to 0.970 g/cm³ in one embodiment, from 0.880g/cm³ to 0.965 g/cm³ in a more particular embodiment, from 0.900 g/cm³to 0.960 g/cm³ in yet a more particular embodiment, from 0.905 g/cm³ to0.955 g/cm³ in yet a more particular embodiment, from 0.910 g/cm³ to0.955 g/cm³ in yet a more particular embodiment, greater than 0.915g/cm³ in yet a more particular embodiment, greater than 0.920 g/cm³ inyet a more particular embodiment, and greater than 0.925 g/cm³ in yet amore particular embodiment.

The polymers derived from the bimodal catalyst and process of theinvention have a bulk density of from 0.400 to 0.900 g/cm³ in oneembodiment, and from 0.420 to 0.800 g/cm³ in another embodiment, andfrom 0.430 to 0.500 g/cm³ in yet another embodiment, and from 0.440 to0.60 g/cm³ in yet another embodiment, wherein a desirable range maycomprise any upper bulk density limit with any lower bulk density limitdescribed herein.

The polymers have a molecular weight distribution, a weight averagemolecular weight to number average molecular weight (M_(w)/M_(n)) offrom 5 to 80 in one embodiment, of from 10 to 60 in a more particularembodiment, of from 15 to 55 in yet a more particular embodiment, and offrom 20 to 50 in yet a more particular embodiment.

The polymers made by the described processes have a melt index (MI) (I₂,as measured by ASTM D-1238, 190/2.16) in the range from 0.01 dg/min to100 dg/min in one embodiment, from 0.01 dg/min to 50 dg/min in a moreparticular embodiment, from 0.02 dg/min to 20 dg/min in yet a moreparticular embodiment, and from 0.03 dg/min to 2 dg/min in yet a moreparticular embodiment, and from 0.002 dg/min to 1 dg/min in yet a moreparticular embodiment, wherein a desirable range may comprise anycombination of any upper I₂ limit with any lower I₂ limit.

Polymers made by the method of the invention have an HLMI (I₂₁, I₂₁ ismeasured by as measured by ASTM-D-1238, 190/21.6) value that ranges from0.01 to 50 dg/min in one embodiment, and from 0.1 to 30 in anotherembodiment, and from 0.5 to 20 in yet a more particular embodiment, andfrom 1 to 10 in yet a more particular embodiment wherein a desirablerange is any combination of any upper I₂₁ limit with any lower I₂₁limit.

Polymers made by the described processes have a melt index ratio (MIR,or I₂₁/I₂) of from 20 to 500 in one embodiment, from 30 to 300 in a moreparticular embodiment, and from 60 to 200 in yet a more particularembodiment. Expressed differently, polymers made by the describedprocesses have a melt index ratio of from greater than 40 in oneembodiment, greater than 50 in a more particular embodiment, greaterthat 60 in yet a more particular embodiment, greater than 65 in yet amore particular embodiment, and greater than 70 in yet a more particularembodiment.

The bimodal polymers produced by the present invention may have acertain average particle size, or APS, ranging from greater than 150microns in one embodiment, and from 150 to 2000 microns in a moreparticular embodiment, and from 150 to 1000 microns in yet anotherembodiment, and from 300 to 800 microns in yet a more particularembodiment. This was determined by using standard sieves. Finesparticles of less than 125 μm) are typically present to less than 5 wt%, or less than 4 wt %, or less than 3 wt %.

In certain embodiments, propylene based polymers can be produced usingthe processes described herein. These polymers include atacticpolypropylene, isotactic polypropylene, hemi-isotactic and syndiotacticpolypropylene. Other propylene polymers include propylene block orimpact copolymers. Propylene polymers of these types are well known inthe art see for example U.S. Pat. Nos. 4,794,096, 3,248,455, 4,376,851,5,036,034 and 5,459,117.

The polymers of the invention may be blended and/or coextruded with anyother polymer. Non-limiting examples of other polymers include linearlow density polyethylenes produced via conventional Ziegler-Natta and/ormetallocene-type catalysis, elastomers, plastomers, high pressure lowdensity polyethylene, high density polyethylenes, polypropylenes and thelike.

Polymers produced by the process of the invention and blends thereof areuseful in such forming operations as film, sheet, pipe and fiberextrusion and co-extrusion as well as blow molding, injection moldingand rotary molding. Films include blown or cast films formed bycoextrusion or by lamination useful as shrink film, cling film, stretchfilm, sealing films, oriented films, snack packaging, heavy duty bags,grocery sacks, baked and frozen food packaging, cable and wiresheathing, medical packaging, industrial liners, membranes, etc. infood-contact and non-food contact applications. Fibers include meltspinning, solution spinning and melt blown fiber operations for use inwoven or non-woven form to make filters, diaper fabrics, medicalgarments, geotextiles, etc. Extruded articles include medical tubing,wire and cable coatings, geomembranes, and pond liners. Molded articlesinclude single and multi-layered constructions in the form of bottles,tanks, large hollow articles, rigid food containers and toys, etc.

More particularly, the polymers made by the method of the invention areuseful in making films. The films may be of any desirable thickness orcomposition, in one embodiment from 1 to 100 microns, and from 2 to 50microns in a more particular embodiment, and from 10 to 30 microns inyet a more particular embodiment; and comprise copolymers of ethylenewith a C₃ to C₁₀ olefin in one embodiment, ethylene with C₃ to C₈α-olefins in a particular embodiment, and ethylene with C₄ to C₆α-olefins in yet a more particular embodiment. The resins used to makethe films may be blended with other additives such as pigments,antioxidants, fillers, etc, as is known in the art, as long as they donot interfere with the desired film properties.

In one embodiment, a film made from one or more of the bimodalpolyolefin compositions disclosed herein has a Dart Drop Impact F50Value of at least 100 [g] on 25.4 micron film and 50 [g] on 12.5 micronfilm; and in a more particular embodiment, the bimodal compositions havea Dart Drop Impact of at least 100 [g] on 25.4 micron film and 75 [g] on12.5 micron film; and in yet a more particular embodiment, the bimodalcompositions have a Dart Drop Impact of at least 200 [g] on 25.4 micronfilm and 100 [g] on 12.5 micron film.

In one embodiment, a film made from one or more of the bimodalpolyolefin compositions disclosed herein has an MD Tear value of atleast 0.8 g/micron on a 25.4 micron film in one embodiment; of at least0.6 g/micron on a 25.4 micron film in a more particular embodiment; andof at least 0.4 g/micron on a 25.4 micron film in yet a more particularembodiment; and less than 5 g/microgram on a 25.4 micron film in yet amore particular embodiment; and less than 5 g/micron on a 25.4 micronfilm in yet a more particular embodiment; and at least 0.2 g/micron on12.5 micron film in one embodiment; at least 0.4 g/micron on 12.5 micronfilm in a more particular embodiment; and at least 0.8 g/micron on 12.5micron film in yet a more particular embodiment; and less than 10g/micron on 12.5 micron film in one embodiment; and less than 5 g/micronon 12.5 micron film a more particular embodiment; wherein a desirablerange of MD Tear values may comprise any upper limit (corresponding to agiven gauge) with any lower limit described herein.

In one embodiment, a film made from one or more of the bimodalpolyolefin compositions disclosed herein has a TD Tear value of at least1.5 g/micron on 24.5 micron film in one embodiment; at least 3 g/micronon 24.5 micron film in a more particular embodiment; and at least 5g/micron on 24.5 micron film in yet a more particular embodiment; and atleast 9 g/micron on 24.5 micron film in one embodiment; and less than 40g/micron on a 24.5 micron film in yet a more particular embodiment, andless than 20 g/micron on a 24.5 micron film in yet a more particularembodiment; and 1.0 g/micron on 12.5 micron film in yet anotherembodiment; 2.0 g/micron on 12.5 micron film in yet a more particularembodiment; 3.0 g/micron on 12.5 micron film in yet a more particularembodiment; and less than 20 g/micron on a 12.5 micron film in yet amore particular embodiment; and less than 15 g/micron on a 12.5 micronfilm in yet a more particular embodiment; wherein a desirable range ofTD Tear values may comprise any upper limit (corresponding to a givengauge) with any lower limit described herein.

The invention can thus be described by any combination of the variousembodiments described above. For example, the method of producing afluorided metallocene catalyst component can be described by thereaction scheme (VI):

-   wherein M is a Group 4, 5 or 6 metal in one embodiment; and    zirconium or hafnium in a particular embodiment;-   each X is independently selected from the group consisting of    chloride, bromide, C₁ to C₂₀ carboxylates, C₂ to C₂₀    acetylacetonates, hydroxide and C₁ to C₁₀ alkoxides in one    embodiment, and more particularly selected from the group consisting    of chloride, bromide, C₁ to C₂₀ carboxylates, C₂ to C₂₀    acetylacetonates;-   R are groups that may replace hydrides on the Cp rings and are    independently selected from groups as defined above; and in a    particular embodiment, selected from the group consisting of C₁ to    C₆ alkyls;-   p is an integer from 0 to 5 in one embodiment, and from 1 to 5 in a    particular embodiment;    -   wherein when p is 2 on any given Cp ring, adjacent R groups may        form ring systems;-   [a]_(a)[β]_(b) is as defined above; and-   the reaction conditions are as defined above in one embodiment, and    more particularly, comprise a two phase system, wherein one phase is    an aqueous phase comprising at least 50 wt % water, at least 80%    water in a particular embodiment; and the other phase comprising a    hydrocarbon or halogenated hydrocarbon diluent.

The present invention also includes a bimetallic catalyst compositioncomprising at least one fluorided metallocene catalyst component asdescribed herein, a non-metallocene catalyst component, and anactivator, the catalyst components and activator supported on aninorganic oxide dehydrated at a temperature of greater than 800° C. Thenon-metallocene component, or “first catalyst component” is desirably aZiegler-Natta catalyst component. The composition is formed in oneembodiment by first synthesizing the fluorided metallocene as describedabove, followed by combining with the non-metallocene catalystcomponent, activator and support in any order. In one embodiment, thenon-metallocene component is first combined with the support followed byan activator, followed then by combining with the fluorided metallocenecatalyst produced by the method described herein.

The present invention also includes a process for producing a bimodalpolyolefin composition comprising the steps of: (a) contacting ametallocene catalyst compound with an fluorinated inorganic salt for atime sufficient to form a fluorinated metallocene catalyst compound;next, (b) isolating the fluorided metallocene catalyst compound;followed by (c) combining the fluorided metallocene catalyst compoundwith an activator and ethylene monomers and optionally a support at from50° C. to 120° C.; and (d) isolating polyethylene. The catalyst may becombined with other monomer such as 1-butene, 1-hexene, etc.

In one embodiment, the fluorided metallocene, activator and support arealso combined with a Ziegler-Natta catalyst comprising titanium halide.This can be done in any desirable order to produce a bimetalliccatalyst. In a particular embodiment, the fluorided metallocene,activator and support are combined and isolated prior to combining withethylene monomers. In another embodiment, the combined fluoridedmetallocene, activator and support are suspended in a diluent comprisingfrom 5 wt % to 100 wt % mineral oil or silicon oil. In a particularembodiment, the fluorinated inorganic salt is characterized in that itgenerates fluoride ions when contacted with a diluent that is at least50 wt % water.

These embodiments of the present invention are exemplified by thefollowing examples.

EXAMPLES Example 1

In the following example, five samples of supported bimetallic catalystswere prepared. Each sample differed primarily in whether a fluorinatedor chlorinated metallocene was used and the dehydration temperature forthe silica support. Specifically, Samples 1 and 4 had the samedehydration temperature (760° C.), but differed in whether fluorinatedor chlorinated metallocene was used, demonstrating a slight increase inpolymer productivity at that temperature (760° C.) due to use of afluoride leaving group rather than a chloride leaving group. Samples 3and 5 demonstrate that the fluorinated metallocene samples that includedsilica dehydrated at temperatures above 800° C. provided surprisinglyhigher catalyst productivity than either chlorinated metallocene sampleshaving silica dehydrated at similar temperatures (Sample 3) orfluorinated metallocene samples having silica dehydrated at lowertemperatures. Specific properties of the samples are displayed in Table1.

Catalyst Preparation. In all the samples, Davidson Sylopol® 955 Silicawas used. Samples 1 and 4 were dehydrated at a temperature of 760° C.;Sample 2 was dehydrated at 830° C.; and Samples 3 and 5 were dehydratedat 875° C. Then, for each sample, a non-metallocene catalyst wascombined with the dehydrated silica. That is, for each sample, 500 gramsof the respective dehydrated silica was added into a 5-liter, 3-neckround bottom flask enclosed in an N₂ glove box. Anhydrous hexane (2500ml) was then added into the flask, making a silica/hexane slurry. Theslurry was heated to a temperature of 54° C. while under constantstirring, and 380 grams of a 15 wt. % solution of dibutyl magnesium wasadded to the slurry over a period of 20 minutes. The slurry was thenallowed to stand for an additional 30 minutes. Butanol (27.4 grams) wasdiluted to volume with hexane in a 125 ml volumetric flask. The entire125 ml of diluted butanol solution was added dropwise into the flaskcontaining the slurry, and then the slurry was held at a temperature of54° C. for 30 minutes while under constant agitation. Titaniumtetrachloride (41.0 grams) was diluted to volume with hexane in a 125 mlvolumetric flask. The entire 125 ml of diluted titanium tetrachloridesolution was then added dropwise into the flask containing the slurry.Following the addition of the solution, the slurry was allowed to standfor 30 minutes at a temperature of 54° C. The slurry was then allowed tocool to ambient temperature to form the “ZN” supported catalyst.

The respective metallocene catalyst compound was then added to eachsample from the above slurry. First, 673 grams of a 30 wt. % solution ofmethylaluminoxane (MAO) in toluene was added to a new flask in an N₂glove box. For Samples 1, 2, and the metallocenebis-n-butyl-cyclopentadienyl zirconium dichloride (13.72 grams) wasadded into the MAO solution and the mixture was stirred until all of thesolids had been dissolved. For Samples 4 and 5, 13.72 grams of themetallocene bis-n-butyl-cyclopentadienyl zirconium difluoride was addedinto the MAO solution, and the mixture was stirred until all of thesolids had been dissolved. Next, the MAO/Metallocene mixture was slowlyadded into the flask containing the previously prepared titaniumreaction slurry over a period of one hour. Toluene (50 ml) was used towash the residual MAO/Metallocene mixture remaining in the flask intothe flask containing the reaction slurry. Each resulting mixture thatincluded the respective bimetallic catalyst sample was then held atambient temperature for a period of one hour. Afterward, each mixturewas dried using a rotary vaporizer, followed by removing most of thehexanes using a vacuum pressure of 21 mmHg at a temperature of 52° C.The high boiling point toluene was subsequently removed using a vacuumpressure of 28 mmHg at a temperature of 70° C. The final driedbimetallic catalyst appeared brown in color as a free flowing solid.Each sample of “ZN/MN” supported catalyst was used in a separatepolymerization run in a gas phase reactor, under the conditionsidentified in Table 1 to form a polyethylene polymer composition.

Fluid-Bed Polymerization. The polymerizations were conducted in acontinuous gas phase fluidized bed reactor. The fluidized bed is made upof polymer granules. The gaseous feed streams of ethylene and hydrogentogether with liquid comonomer were mixed together in a mixing teearrangement and introduced below the reactor bed into the recycle gasline. Monomers of 1-hexene were used as the comonomer. The individualflow rates of ethylene, hydrogen and comonomer were controlled tomaintain fixed composition targets. The ethylene concentration wascontrolled to maintain a constant ethylene partial pressure. Thehydrogen was controlled to maintain a constant hydrogen to ethylene moleratio. The concentration of all the gases were measured by an on-linegas chromatograph to ensure relatively constant composition in therecycle gas stream.

The solid catalyst was injected directly into the fluidized bed usingpurified nitrogen as a carrier. Trimethylaluminum (TMA) was added as acocatalyst for the ZN catalyst. Its rate was adjusted to maintain aconstant production rate. The reacting bed of growing polymer particlesis maintained in a fluidized state by the continuous flow of the make upfeed and recycle gas through the reaction zone. A superficial gasvelocity of 1-3 ft/sec was used to achieve this. The reactor wasoperated at a total pressure of 300 psig. To maintain a constant reactortemperature, the temperature of the recycle gas is continuously adjustedup or down to accommodate any changes in the rate of heat generation dueto the polymerization.

The fluidized bed was maintained at a constant height by withdrawing aportion of the bed at a rate equal to the rate of formation ofparticulate product. The product is removed semi-continuously via aseries of valves into a fixed volume chamber, which is simultaneouslyvented back to the reactor. This allows for highly efficient removal ofthe product, while at the same time recycling a large portion of theunreacted gases back to the reactor. This product is purged to removeentrained hydrocarbons and treated with a small steam of humidifiednitrogen to deactivate any trace quantities of residual catalyst.

Resin Properties. The properties of the polymer was determined by thefollowing test methods:

-   -   1. Melt Index: ASTM D-1238-Condition E,    -   2. Density: ASTM D-105,    -   3. Bulk Density: The resin is poured via a ⅞ inch diameter        funnel into a fixed volume cylinder of 400 cc. The bulk density        is measured as the weight of resin divided by 400 cc to give a        value in g/cc,    -   4. Particle Size: The particle size is measured by determining        the weight of material collected on a series of U.S. Standard        sieves and determining the weight average particle size based on        the sieve series used.        The fines are defined as the percentage of the total        distribution passing through a 120 mesh standard sieve. This has        a particle size equivalent of 120 microns. Fines are important        since high levels can lead to sheeting and fouling of the        reaction cycle gas system. This results in heat exchanger        distributor plate fouling requiring a reactor shut down to clean        out.

Each run was operated over a period of 24 hours, as indicated in Tables1 and 3. Each run was conducted using the same continuous gas phasefluidized bed reactor. The fluidized bed of that reactor was made up ofpolymer granules. During each run, the gaseous feed streams of ethyleneand hydrogen were introduced below the reactor bed into a recycle gasline. Hexene comonomer was introduced below the reactor bed. Theindividual flows of ethylene, hydrogen and hexene comonomer werecontrolled to maintain fixed composition targets, identified in Tables 1and 3. The concentrations of gases were measured by an on-linechromatograph.

Example 2

Resins produced from the catalysts in Example 1 were compounded on aZSK-30 compounder with an additive package of 1500 ppm Irganox 1010,1500 ppm Irgafos 168 and 1500 ppm zinc stearate. The compoundingoperation was conducted under a nitrogen blanket, and conditions wereadjusted to maintain the melt temperature below 230° C. Films made fromthe polymers were formed for purposes of assessing polymer properties.The following example describes the fabricating conditions for the filmfabrication process. Films were fabricated on an Alpine blown film linewith a single 50 mm grooved extruder. The die was 100 mm in diameter andhad a 1 mm die gap. Extrusion was conducted at a rate of 45.4 kg/hr,while maintaining a temperature profile of 201/204° C. on the extruderand a flat temperature profile of 210° C. on the die. The film was blownat a 4:1 blow up ratio (BUR), with an initial gauge of 25 microns and afrost line height of 90 cm using chilled air without using an internalbubble stabilizer bar or an internal bubble cooling. The take-up speedwas gradually increased until either the maximum take-up speed of thewinder was reached or the onset of the bubble instability was noted.Physical properties, reported in Table 2 were measured on stable bubblesof gauges 25 and 12 microns using standard ASTM techniques. ElmendorfTear Strength values were measured in the MD and TD direction inaccordance with ASTM D1922-00. Dart Drop Impact F50 values were measuredusing the procedures in ASTM D1709-00.

The present invention offers many advantages over the prior art. Oneadvantage is that the catalyst system offers improved catalystproductivity in polyethylene production. More particularly, the silicasupported titanium-based Ziegler Natta/fluorided metallocene catalysthas an activity of from greater than 4500 g/g in one embodiment, andgreater than 5000 g/g in a more particular embodiment, and greater than5400 g/g in yet a more particular embodiment at a polymerizationtemperature of from 90 to 100° C. in one embodiment, and from 93 to 98°C. in a more particular embodiment. This is a higher activity than forthe corresponding chlorided metallocene (Samples 1-3) and even thechlorided metallocenes with the enhanced silica support (Samples 2-3).

The catalyst and method of the present invention also offers theadvantage of producing polyethylene polymers having bulk densitiesranging from 0.420 to 0.500 g/ml in one embodiment, and ranging from0.440 to 0.490 g/ml in another embodiment, and ranging from 0.450 to0.480 g/ml in yet a more particular embodiment; and particularly when ansilica support is used that has been dehydrated at from 830° C. or morein particular embodiments.

These results are accomplished using a molar ratio of hydrogen toethylene as described herein, and more particularly of from 0.001 to0.015 in one embodiment, and from 0.002 to 0.010 in another embodiment,and from 0.003 to 0.009 in yet another embodiment, and from 0.004 to0.008 in yet another embodiment, wherein a desirable range may compriseany combination of any upper mole ratio limit with any lower mole ratiolimit described herein.

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to many differentvariations not illustrated herein. For these reasons, then, referenceshould be made solely to the appended claims for purposes of determiningthe scope of the present invention. Further, certain features of thepresent invention are described in terms of a set of numerical upperlimits and a set of numerical lower limits. It should be appreciatedthat ranges formed by any combination of these limits are within thescope of the invention unless otherwise indicated.

Unless otherwise indicated, all numbers expressing quantities ofingredients, properties, reaction conditions, and so forth, used in thespecification and claims are to be understood as approximations based onthe desired properties sought to be obtained by the present invention,and the error of measurement, etc., and should at least be construed inlight of the number of reported significant digits and by applyingordinary rounding techniques. Notwithstanding that the numerical rangesand values setting forth the broad scope of the invention areapproximations, the numerical values set forth are reported as preciselyas possible.

All priority documents are herein fully incorporated by reference forall jurisdictions in which such incorporation is permitted. Further, alldocuments cited herein, including testing procedures, are herein fullyincorporated by reference for all jurisdictions in which suchincorporation is permitted.

TABLE 1 Reaction Conditions and Resin Properties Parameter 1 2 3 4 5Catalyst ZN/MN- ZN/MN- ZN/MN- ZN/MN- ZN/MN- Description dichloridedichloride dichloride difluoride difluoride Catalyst Dehydration 760 830875 760 875 Temp. (° C.) Residence Time (hrs) 3.9 3.1 2.8 3.3 3.3 C₂Partial Pressure 157.1 157.1 157.3 156.5 155.7 (psia) H₂/C₂ anz ratio110.5 108.0 110.0 112.2 107.3 (ppm/%) C₆/C₂ anz ratio (%/%) 0.010 0.0100.010 0.011 0.010 Bed Temperature (° C.) 95 95 95 95 95 Production Rate55.8 69.4 75.7 69.8 70.2 (lb/hr) Catalyst Productivity 2594 3603 40002881 5564 (g/g) TMA/C₂ Flow Ratio 121.4 122.0 124.7 124.9 124.9 (wt ppm)H₂O/C₂ Flow Ratio 20.1 24.7 27.0 13.0 23.6 (wt ppm) Resin Properties I₂[g/10 min] 0.051 0.061 0.055 0.064 0.061 I₂₁ [g/10 min] 5.58 5.32 5.587.73 6.92 I₂₁/I₂ 110.0 87.2 97.5 120.7 118.4 Density (g/cm³) 0.95070.9518 0.9538 0.9528 0.9506 Bulk Density (g/cm³) 0.4005 0.4168 0.45330.4160 0.4715 APS [microns] 630 653 609 579 661 Fines (<125 μm) (%) 3.12.0 1.9 3.8 3.3

TABLE 2 Film Properties Property Units 1 2 3 4 5 Amperage amps 59.4 60.159.9 59.9 60.4 Pressure MPa 50.2 49.5 50.8 46.4 46.4 Max Draw m/min 54.951.8 57.9 51.8 51.8 Down Gauge microns 25.4 12.7 25.4 12.7 25.4 12.725.4 12.7 25.4 13 Dart Drop g 344 344 335 296 317 266 287 269 341 326Impact F50 MD Tear g/micron 1.01 0.97 1.18 0.76 1.38 1.02 0.92 0.84 1.051.00 TD Tear g/micron 9.40 1.91 9.38 2.91 7.66 2.49 10.69 3.64 11.973.80

1. A bimetallic catalyst composition comprising a fluorided metallocenecatalyst component, a non-metallocene catalyst component, and anactivator, the catalyst components and activator supported on aninorganic oxide dehydrated at a temperature of 870° C. or more.
 2. Thebimetallic catalyst composition of claim 1, wherein the fluoridedmetallocene compound is described by the formulas:Cp^(A)Cp^(B)MX_(n), Cp^(A)MX_(n) or Cp^(A)(A)Cp^(B)MX_(n) wherein M is aGroup 4, 5 or 6 atom; Cp^(A) and Cp^(B) are each bound to M and areindependently selected from the group consisting of cyclopentadienylligands, substituted cyclopentadienyl ligands, ligands isolobal tocyclopentadienyl and substituted ligands isolobal to cyclopentadienyl;(A) is a divalent bridging group bound to both Cp^(A) and Cp^(B)selected from the group consisting of divalent C₁ to C₂₀ hydrocarbylsand C₁ to C₂₀ heteroatom containing hydrocarbonyls; wherein theheteroatom containing hydrocarbonyls comprise from one to threeheteroatoms; at least one X is a fluoride ion; and n is an integer from1 to
 3. 3. The bimetallic catalyst composition of claim 1, wherein themetallocene compound is described by the formulas:Cp^(A)Cp^(B)MX_(n) or Cp^(A)(A)Cp^(B)MX_(n) wherein M is zirconium orhafnium; Cp^(A) and Cp^(B) are each bound to M and are independentlyselected from the group consisting of substituted cyclopentadienylligands, substituted indenyl ligands, substituted tetrahydroindenylligands, substituted fluorenyl ligands, and heteroatom derivatives ofeach; wherein the substituent groups are selected from the groupconsisting of C₁ to C₁₀ alkyls and halogens; (A) is a divalent bridginggroup bound to both Cp^(A) and Cp^(B) selected from the group consistingof divalent C₁ to C₂₀ hydrocarbyls and C₁ to C₂₀ heteroatom containinghydrocarbonyls; wherein the heteroatom containing hydrocarbonylscomprise from one to three heteroatoms; at least one X is a fluorideion; and n is an integer from 1 to
 3. 4. The bimetallic catalystcomposition of claim 2 or 3, wherein at least one Cp is substituted. 5.The bimetallic catalyst composition of claim 2 or 3, wherein at leastone Cp is disubstituted.
 6. The bimetallic catalyst composition of claim2 or 3, wherein at least one Cp has from 2 to 5 substitutions.
 7. Thebimetallic catalyst composition of claim 6, wherein the substituentgroups are selected from the group consisting of methyl, ethyl,n-propyl, iso-propyl, n-butyl, iso-butyl, and tert-butyl.
 8. Thebimetallic catalyst composition of claim 1, wherein the bimetalliccatalyst also includes a Ziegler-Natta catalyst component.
 9. Thebimetallic catalyst composition of claim 8, wherein the Ziegler-Nattacatalyst component comprises a compound selected from the groupconsisting of Group 4 and Group 5 halides, oxides, oxyhalides,alkoxides, and mixtures thereof.
 10. The bimetallic catalyst compositionof claim 1, wherein the inorganic oxide is silica.
 11. A bimetalliccatalyst composition comprising a fluorided metallocene catalystcomponent, a non-metallocene catalyst component, and an activator, thecatalyst components and activator supported on an inorganic oxidedehydrated at a temperature of 870° C. or more; wherein the metallocenecompound is described by the formulas:Cp^(A)Cp^(B)MX_(n) or Cp^(A)(A)Cp^(B)MX_(n) wherein M is zirconium orhafnium; Cp^(A) and Cp^(B) are each bound to M and are independentlyselected from the group consisting of substituted cyclopentadienylligands, substituted indenyl ligands, substituted tetrahydroindenylligands, substituted fluorenyl ligands, and heteroatom derivatives ofeach; wherein the substituent groups are selected from the groupconsisting of C₁ to C₁₀ alkyls and halogens; (A) is a divalent bridginggroup bound to both Cp^(A) and Cp^(B) selected from the group consistingof divalent C₁ to C₂₀ hydrocarbyls and C₁ to C₂₀ heteroatom containinghydrocarbonyls; wherein the heteroatom containing hydrocarbonylscomprise from one to three heteroatoms; at least one X is a fluorideion; and n is an integer from 1 to 3.